United States Environmental Protection Agency
Region 2
RCRA Outreach Program
EPA-902-B-96-001
Revised June 25, 1996
TECHNICAL ASSISTANCE DOCUMENT
FOR COMPLYING WITH THE TC RULE
AND IMPLEMENTING THE TOXICITY
CHARACTERISTIC LEACHING
PROCEDURE (TCLP)
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TECHNICAL ASSISTANCE DOCUMENT FOR
COMPLYING WITH THE TC RULE AND
IMPLEMENTING THE TOXICITY
CHARACTERISTIC LEACHING PROCEDURE (TCLP)
The following individuals prepared Chapter 1:
John Hansen
Hazardous Waste Compliance Branch
Air and Waste Management Division
USEPA Region 2 -
26 Federal Plaza
New York, New York 10278
Claudette Reed
Hazardous Waste Compliance Branch
Air and Waste Management Division
USEPA Region 2
26 Federal Plaza
New York, New York 10278
Michael Scudese
TRC Environmental Corporation
18 World's Fair Drive
Somerset, New Jersey 08873
Edited by: Frank Langone, IBM Corporation
Route 134, Yorktown Heights, New York 10598
The following individuals prepared Chapters 2 to 6:
Leon Lazarus Mitzi Miller
Monitoring Management Branch Environmental Quality Management
Environmental Services Division 10801 Fox Park
USEPA Region 2 Khoxville, Tennessee 37931
2890 Woodbridge Avenue
Edison, New Jersey 08837
Edited by: Frank Langone, IBM Corporation
Route 134, Yorktown Heights, New York 10598
May 1994
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References herein to any specific commercial product, process or service by trade
name, manufacturer, or otherwise does not imply its endorsement or
recommendation by EPA, TRC or EQM.
in
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IV
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Acknowledgements
The authors would like to thank the following individuals
for peer reviewing: this document:
Kate Anderson, USEPA Office of Waste Programs Enforcement
Dr. Bill Batchelor, Texas A&M University
Edwin Barth, USEPA Center for Environmental Research
Dr. Ha Cote, USEPA Health Effects Research Laboratory
Phil Rax, USEPA Region 2
Oliver Fordham, USEPA Office of Solid Waste
Kathleen Grimes, NJDEPE Bureau of Environmental Measurements
and Quality: Assurance
Dr. Larry Jackson, Environmental Quality Management
Kevin Kubik, USEPA Region 2
Frances Liem, USEPA Office of Compliance Monitoring
Davis Jones, USEPA Office of Waste Programs Enforcement
Rose Lew, USEPA Office of Waste Programs Enforcement
Ken Peist, USEPA Region 2
•
Dr. Roger Spence, Oak Ridge National Laboratories
Gale Sutton, Galson Laboratories
Rock Vrtale, Environmental Standards
Dr. Ken Wilkowski, USEPA Office of Research and Development
Dr. Lew Williams, USEPA Environmental Monitoring Systems Laboratory
Appreciation is also expressed for technical contributions from:
Jennifer Brarnlett, SAIC Corporation
Dr. Mike Maskarinec, Oak Ridge National Laboratory
Carla Stout, TRC Environmental Corporation
Ted Varouxis, Associated Design and Manufacturing
the supplier of equipment and training tapes for the course
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Document Introduction
The goal of this document is to assist the regulated community to make proper utilization of
the Toxicity Characteristic Leaching Procedure (TCLP) to demonstrate compliance with the
Toxicity Characteristic (TC) and Land Ban Regulations. The following issues will be
discussed:
What is TCLP?
• When must TCLP be performed?
• Which analyte lists should be used to demonstrate compliance with TC and Land Ban
regulations?
• How should a sampling strategy be developed?
• How much QA/QC and analytical deliverables are appropriate?
• How should one use the USEPA Region 2 TCLP data validation criteria?
• How should sampling plans be developed for multi-phase and oily materials?
The following topics were added to the 1994 version of this document:
• Obtaining CAMU variances from the Land Ban regulations.
• Inappropriateness of TCLP method for risk assessments.
• Characterizing heterogeneous solid wastes.
• Characterizing building demolition debris containing lead based paint.
• Implications of classifying non-hazardous wastes as hazardous.
• Region 2 State TCLP policy guidances.
VI
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VII
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TABLE OF CONTENTS
Chapter Page
1.0 COMPLYING WITH THE TC RULE 1-1
1.1 Introduction 1-2
1.2 RCRA OVERVIEW 1-3
1.2.1 Growth of Hazardous Waste in America: The Case of Love Canal 1-3
1.2.2 RCRA Cradle to Grave Concept 1-5
1.2.3 Definitions of Hazardous Waste t-8
1.2.4 Making a Hazardous Waste Determination 1-10
1.3 THETOXICJTY CHARACTERISTIC RULE 1-11
1.3.1 EP Tox Test 1-11
1.3.2 TCLP Test 1-12
1.3.3 TC Rule's Effect Upon Generators and TSDFs 1-14
1.4 TC RULE'S EFFECT ON INDIVIDUAL RCRA REGULATIONS 1-18
1.4.1 General 1-18
1.4.2 Corrective Action and Closure 1-19
1.4.3 Land Disposal Restrictions (LDR) 1-20
1.4.4 Minimum Technology Requirements for Landfills and Surface
Impoundments ; 1-21
1.4.5 Exemption for Tanks (Minimum Technology Requirements) 1-22
1.4.6 Mixture Rule Exemption 1-23
1.4.7 Previously Delisted Wastes 1-24
1.4.8 Special Waste Exemptions 1-25
1.4.9 Hazardous Waste Listings 1-26
1.4.10 "Mixture' and "Derived From" Rules 1-27
1.4.11 Excluded Wastes 1-28
1.5 IMPACT OF TC RULE ON OTHER EPA PROGRAMS 1-29
1.5.1 Underground Storage Tanks (USTs) 1-29
1.5.2 Comprehensive Environmental Response and Liability .Act (CERCLA) ... 1-31
1.5.3 Clean Water Act (CWA) 1-32
1.5.4 Safe Drinking Water Act (SDWA) 1-34
1.5.5 Federal Insecticide, Fungicide, and Rodenticide Act (FIFRA) 1-37
1.5.6 Used Oil Recycling Act 1-38
1.5.7 Toxic Substances Control Act (TSCA) 1-39
1.6 POLLUTION PREVENTION 1-40
1.7 CONCLUSIONS 1-43
VIII
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TABLE OF CONTENTS (Continued)
Chapter Page
2.0 APPLICATIONS OF THE TCLP METHOD 2-1
2.1 What is TCLP? 2-4
2.2 When is the Use of TCLP Applicable? 2-3
2.3 When is the Use of TCLP Inappropriate? 2-9
2.4 Sampling and Analysis Design 2-12
3.0 TC AND TCLP PROJECT PLANNING 3-1
3.1 Data Quality Objectives 3-2
3.2 DQO Case Study: Cadmium Contaminated Fly Ash Waste 3-10
3.3 Sampling and Analysis Design 3-18
3.4 Analytical Method Selection 3-22
4.0 OVERVIEW OF THE TCLP METHOD 4-1
4.1 Preliminary Sample Preparation for Leaching 4-2
4.2 Leaching Procedure for Nonvolatiles 4-5
4.3 Leaching Procedure for Volatiles 4-11
4.4 TCLP Method Quality Control 4-15
5.0 DATA VALIDATION AND DELIVERABLES 5-1
5.1 Data Validation 5-2
5.2 Data Deliverables 5-6
6.0 ANALYZING AND ASSESSING MULTI-PHASIC AND OILY WASTES 6-1
6.1 Definition of Oily Waste 6-2
6.2 Problems/Issues 6-3
6.3 Suggestions 6-5
6.4 Most Commonly Asked TCLP Question 6-7
6.5 Analytical Options 6-14
IX
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TABLE OF CONTENTS (Continued)
TABLES
Table Page
1-1 TC Rule Constituents 1-13
1-2 Permit Modifications 1-17
2-1 Toxicity Characteristic Constituents - Alphabetical . 2-10
3-1 TCLP Holding-Times 3-20
3-2 TC Analytes and Their Regulatory Levels . 3-23
3-3 Metals Analysis Method By ICP 3-25
3-4 Metals Analysis Methods by GFAA and Mercury by CVAA 3-25
3-5 Pesticide and Herbicide Quantitation Limits by SW 846 and CLP 3-26
3-6 Quantitation Limits for Volatile TC Constituents 3-27
3-7 Quantitation Limits for Semivolatile TG Constituents 3-28
4-1 Volume of Extract Required for One Nonvolatile Analysis 4-7
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TABLE OF CONTENTS (Continued)
FIGURES
Figure /Page
3-1 Overview of the Data Quality Objectives Planning .Process ... 3^5
3-2 Decision Performance Curve for Cadmium Fly-Ash Waste Example ;....... 3-57
4-1 TCLP Preliminary Determinations 4-4
4-2 Nonvolatile Extraction 4-6
4-3 Volatiles by ZHE 4-12
4-4 Volatiles by ZHE Continued 4-13
4-5 Standard,Addition Plot 4-17
XI
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TABLE OF CONTENTS (Continued)
APPENDICES
Appendix
I TCLP Method 1311 (July 1992, Revision 0)
IV USEPA Region 2 Organic, Inorganic and TCLP Data Validation SOPs
V References for Multi-phasic and Oily Waste
VI Office of Solid Waste Management Methods Section Memoranda #35, #36
VII Recommendations and Rationale for Analysis of Contaminant Release by the
Environmental Engineering Committee, Science Advisory Board, October 1991
VIII USEPA Region 2 Special Analytical Services Request
IX Required Uses of SW 846
X Stabilization/Solidification: Is It Always Appropriate? and Stabilization/Solidification of
Wastes Containing Volatile Organic Compounds in Commercial Cementitious Waste
Forms from: Stabilization and Solidification of Hazardous, Radioactive, and Mixed
Wastes, Second Volume, ASTM STP 1123
XI Army Waste Classification Guidance for Building Demolition Debris Containing Lead
Based Paint
XII 1992 Workshop on Characterizing Heterogeneous Materials .
XIII Improper Hazardous Waste Characterizations: Financial and Compliance Implications
XIV Region 2 State TCLP Guidances
XII
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XIII
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List of Abbreviations and Acronyms
AC Alternating Current
ARARs Applicable or Relevant and Appropriate Requirements
ASTM American Society of Testing and'Materials
BOAT Best Demonstrated Available Technology
SNA Base, Neutral and Acid Extractable Organics
CAMU Corrective Action Management; Unit
CBEC Concentration Based Exemption Criteria
CCWE Constituent Concentrations in Waste Extracts
CERCLA Comprehensive Environmental Response Compensation 'and Liability Act of 1980
CESQG Conditionally Exempt Small Quantity ^Generator
GFR Code of Federal Regulations
CLP Contract Laboratory Program
COC Chain of Custody
CRDL Contract Required Detection'Limits
CTRL Chronic Toxicity Reference Levels
CVAA Cold Vapor Atomic Adsorbtion
CWA Clean Water Act
DAP Dilution Attenuation Factor
DC Direct Current
DQO Data Quality Objectives
DQOPP Data Quality Objectives Planning Process
FAA Flame Atomic Adsorbtion
RFRA Federal Insecticide, Fungicide, and Rbdenticide Act
EP Tox Extraction Procedure Toxicity .
EQL Estimated Quantitation Limit *
GFAA Graphite Furnace Atomic Absorption
HAZWRAP Hazardous Waste Remedial Action Program
HSWA Hazardous Solid Waste Amendments
HWN Hazardous Waste Numbers . .
P designates Acute Toxicity
U designatesToxic Waste
K designates Process Waste
F designates Generic Source Waste
D designates Characteristic Waste
ICP Inductively Coupled Plasma
LDR Land Disposal Restrictions
LOG Large Quantity Generator
MCL Maximum Contaminant Level
MCLG Maximum Contaminant Level Goals .
MS Matrix Spike
MSD Matrix Spike Duplicate
NIPDWS National Interim Primary Drinking Water Standards
NPDES National Pollutant Discharge Elimination System
PCB Polychlbrinated Biphenyls
POHC Principal Organic Hazardous Constituent
POTWs Publidy Owned Treatment Works
PPIG Pollution Prevention I nfornration Clearinghouse
PPIES Pollution Prevention Information Exchange System
PQL Practical Quantitation Limit'
QA Quality Assurance
QAMS Quality Assurance Management Staff
QC Quality Control
RA Regional Administrator
XIV
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List of Abbreviations and Acronyms (Continued)
RCRA Resource Conservation and Recovery Act
RR RCRA Facility Investigation
RSD Risk Specific Doses
RfD Referenced Doses
SDWA Safe Drinking Water Act
SQG Small Quantity Generator
SW-846 Solid Waste Procedures
TC Toxicity Characteristic
TCLP Toxicity Characteristic Leaching Procedure
TIC Tentatively Identified Compound
TSCA Toxic Substances Control Act
TSDF Treatment Storage and Disposal Facility
UIC Underground Injection Control
USDW Underground Sources of Drinking Water
UST Underground Storage Tank
VOA Volatile Organic Analysis
ZHE Zero Headspace Extraction
xv
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o
Q)
•O
i-+
CD
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Chapter 1
COMPLYING WITH THE TC RULE
Introduction
RCRA Overview
The Toxicity Characteristic Rule
TC Rule's Effect on Individual RCRA Regulations
Impact on Other RCRA Programs
Pollution Prevention
Conclusions
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1.0 COMPLYING WITH THE TOXICltY CHARACTERISTIC RULE
The purpose of this chapter is to provide an understanding of the Toxicity
Characteristic (TCJ Rule, as it;relates to nazardqus.v/aste management under the
Resource Conservation and Recovery Art (RGRA). The development .of
hazardous waste issues in the United States is discussed first, giving the example
of Love Canal, which is a case study of an uncontrolled hazardous waste site.
Then an overview of RCRA is presented, With a comparison of the Extraction
Procedure Toxicrty (EP.Tox)Test and;tjie T^GRujej including the Toxicity
Characteristic Leaching Procedure, (f(XP) is presented! Finally,:the impact of the
TC Rule oh RCI^ and non-RGRATegulations is discussed.
1-1
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1.1 Introduction
Hazardous waste growth in America.
RCRA system to control hazardous waste disposal.
Determination of hazardous waste by testing.
Changes to the testing procedure for hazardous waste. 1C Rule replaces
the EP Tox Test
Purpose of the manual.
In America, about 500,000 companies generate approximately 170,000 metric tons of
hazardous waste annually.
In 1976, the Resource Conservation and Recovery Act (RCRA) was passed for proper
management of hazardous waste to protect human health and the environment.
The extraction procedure toxicity (EP Tox) test was one of the analytical methods
used to ascertain if a waste was hazardous.
The Toxicrty Characteristic Leaching Procedure (TCLP) replaced the EP Tox test when
determining if a solid waste is hazardous because it exhibits the toxicity characteristic.
1-2
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1.2 RCRA OVER VIEW
1.2.1 Growth of Hazardous Waste in America: The Case of Love Canal
• America in the 1890s.
• The invention of electricity.
• New chemicals.
• Clustering of industries around power sources.
Building of Love Canal to connect the lower and upper parts of Niagara
Falls.
DC power versus AC power.
America in the 1890s was undergoing industrialization. With the invention of electric
power, new chemicals were developed. A widely used chemical process was the
electrolysis of sodium chloride (salt) to yield sodium hydroxide (lye), chlorine and
hydrogen. Lye was mixed with waste animal fat from slaughter houses to produce
soap. Ivory soap is still made this way. Chlorine, originally a useless byproduct,
eventually was utilized as a raw material in the production of chlorinated solvents and
pesticides. These chemicals had toxic effects which were not then understood.
Direct current (DC) electricity was used for this electrolysis process. Industries in the
1890s which used significant quantities of electricity had to cluster around their DC
power sources because DC electricity does not travel efficiently.
In Niagara Falls, a hydroelectric dam generated low cost electrical energy. Industries
were clustered in the area to obtain inexpensive DC power. Construction commenced
on the Love Canal industrial transportation network to connect the lower and upper
parts of the Niagara Falls area.
However, when alternating current (AC) electricity was invented, electricity travelled
much further over power lines. Thus, it was no longer necessary to cluster industries
around the Niagara Falls area, and the Love Canal project was abandoned. Love
Canal was subsequently used by industry as a hazardous waste dump, and leached
toxic contaminants into the surrounding ground water and soil. Even after Love Canal
was capped and closed, toxic chemicals continued to leach out.
Most of the discarded hazardous chemicals were contained in the clay-lined Love
Canal until school and highway construction ruptured the walls. This fracturing of the
walls caused chemicals to contaminate local homes and the school built directly over
the dump site. People living in the area started to experience health problems,
including miscarriages, stillbirths, and chromosome damage.
1-3
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• In 1980, President Jimmy Carter evacuated approximately 700 families out of the Love
Canal area to protect their health.
» The purpose of RCRA is to prevent this type of inadequate hazardous waste
management.-.
1-4
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1.2.2 RCRA Cradle to Grave Concept
RCRA tracks hazardous waste from cradle to grave:
the manifest system.
Components:
generator
transporter
treatment storage and disposal facility (TSDF).
Anyone generating hazardous waste must notify EPA:
generator definition.
RCRA is considered a "cradle to grave" system because it regulates the handling of
hazardous waste from creation to disposal. This ensures that hazardous waste is
handled properly, and does not contaminate the environment
There are three hazardous waste handler classifications: the generator, who creates
the hazardous waste; the transporter, who transports the hazardous waste to the
ultimate disposal site; and the ultimate disposal site, which is called a treatment,
storage and disposal facility (TSDF). Final disposition of hazardous waste often
occurs after interim storage/treatment/recycling operations at several sites.
Facilities that generate solid waste must determine if their solid waste is a hazardous
waste.
Facilities that generate hazardous waste must notify EPA or the authorized State
agency, and obtain an EPA facility identification number (EPA ID number).
/
The EPA or an authorized state agency issues an EPA ID number to make unique
identification of each TSDF which handles hazardous waste.
Hazardous waste generators must manage hazardous waste according to RCRA
regulations. The generator must dispose of hazardous waste properly, and must
complete a manifest enumerating the contents of the waste.
The generator is responsible for using authorized transporters and disposal facilities.
The generator can usually store hazardous waste on site for up to 90 days without a
storage permit.
1-5
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Generator responsibilities:
Determination of hazardous waste
Notify EPA
Obtain EPA ID number
Prepare manifest
Dispose of waste using an authorized transporter and an
authorized TSDF
Accumulation time
Annual reports
Contingency plans/Training requirements
Generator categories - CESQG/SQG/LQG
RCRA enforcement:
State versus Federal
The generator must file bi-annual reports detailing the amount of waste disposed.
EPA generator categories (many states have different generator categories):
LOG - Large quantity generators (LOG) generate more than 1000 kilograms
(kg) of hazardous waste/month or more than 1 kg of acutely hazardous
waste/month. LQGs are fully regulated and must comply with all
generator requirements indicated above.
SQG - Small quantity generators (SQG) are generators which:
Generate between 100 and 1,000 kg/month of hazardous waste.
Accumulate no more than 6,000 kg of hazardous waste on site
at any one time.
Accumulate hazardous waste on site for up to 180 days or 270
days if the disposal site for the waste is over 200 miles away.
Provide notification of hazardous waste activities, use manifests
to dispose of hazardous waste, and dispose of hazardous waste
at TSDFs, but do not file annual reports.
1-6
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CESQG - Conditionally exempt small quantity generators (CESQG) are
generators which:
Generate jess than 100 kg/month non-acute hazardous
waste per calendar month or;
Generate Jess than 1 kg/month acutely hazardous waste
(P-waste;code). There are also several acutely
hazardous F-listed wastes.
May never accumulate more than 1,000 kg of hazardous
waste or greater than 1 kg of acutely hazardous waste at
any time. If they do, they will be regulated as a SQG.
Are subject to reduced requirements. SQGs do not need
to notify EPAror State agencies, use manifests, or
dispose of their hazardous waste in a TSDF (they may
use a municipal or industrial landfill).
RCRA enforcement:
EPA has delegated RCRA enforcement authority to many states. In those
states, the hazardous waste regulations may not be less strict than EPA's
regulations. Some states have regulations which are more stringent than
EPA's. . .-"''' -.•'•""" . "' ;._ ""•'
EPA however, retains overall jurisdiction over all state RCRA programs.
1-7
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1.2.3 Definitions of Hazardous Waste
Only wastes classified as 'solid wastes" may be characterized as
"hazardous wastes".
The definition of hazardous waste has four parts:
"Statutory definition"
"Listed waste" - Four lists: F, K, U, P
"Mixture rule" - Defines hazardous waste as being a mixture of a
hazardous waste and a non-hazardous waste.
"Characteristic waste"
Ignitabie
Corrosive
Reactive
Toxic - (TC Rule)
Only wastes classified as "solid wastes" may be characterized as "hazardous wastes/
Definition of solid waste:
"The term solid waste means any garbage, refuse, or sludge, from a waste
treatment plant, water supply treatment plant, or air pollution control facility;
and other discarded material, including solid, liquid, semisolid, or contained
gaseous material resulting from industrial, commercial, mining, and agricultural
operations, and from community activities, but does not include solid or
dissolved materials in irrigation return flows or industrial discharges which are
point sources subject to permits under Section 402 of the Federal Water
Pollution Control Act, as amended Statute 880; or source, special nuclear, or
byproduct material as defined by the Atomic Energy Act of 1954, as amended
(68 Statute 923).*
Definition of hazardous waste:
The term 'hazardous waste' means a solid waste, or combination of solid
wastes, which because of its quantity, concentration, or physical, chemical or
infectious characteristics may:
(A) cause, or significantly contribute to an increase in mortality or an
increase in serious irreversible, or incapacitating reversible, illness; or
(B) pose a substantial present or potential hazard to human health or the
environment when improperly treated, stored, transported, or disposed
of, or otherwise managed.12
1 42 United States Code (USC) 6903, Section 1004(27)
2 - Ibid, (5)
1-8
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Regulatory Definitions:
• Listed hazardous waste - Wastes classified as hazardous because of how they were
produced. There are four lists of hazardous waste: F, K, U, and P.
Four types of listed waste:
F Waste - List of waste from non-specific sources
K Waste • List of waste from specific sources
U Waste - List of discarded chemical products
P Waste - List of acutely toxic discarded chemical products
• Mixture rule - Any mixture of a listed hazardous waste and a non-hazardous waste is
considered hazardous.
• Derived from rule - See 40 CFR 261.3c.
• Characteristic waste - Four characteristics are utilized to determine if a solid waste,
which is not a listed hazardous waste, is classified as a hazardous waste.
• Characteristic of ignitabiltty:
A flashpoint of < 140°F
For non-liquids - if the waste, when ignited, can burn spontaneously
An ignitable compressed gas
An oxidizer as defined in 49 CFR 173.151
• Characteristic of corrosivity:
The waste is aqueous and pH <_ 2 or j>. 12.5.
The waste corrodes steel at a rate of j> 6.35 millimeters/year.
• Characteristic of reactivity:
The waste is unstable and undergoes violent reaction.
The waste reacts violently with water.
The waste, when heated, is explosive.
The waste, when mixed with water, releases toxic gases.
The waste contains cyanide or a sulfide, and releases toxic gases when
exposed to pH conditions between 2 and 12.5.
The waste can explode if shocked or heated.
The waste is defined as an explosive by U.S. Department of Transportation
regulations.
o Characteristic of toxicity - A waste exhibits the characteristic of toxicity if the
concentration of one or more of the 39 toxicity characteristic analytes in the TCLP
aqueous extract exceeds regulatory action levels. This is known as the TC Rule. This
replaces the EP Tox Test, which contained 8 inorganic and 6 organic constituents.
Note: If wastes are listed solely because they exhibit a characteristic, and the
resulting mixture no longer exhibits a characteristic, the material is no longer a
hazardous waste.
1-9
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1.2.4 Making a Hazardous Waste Determination
Does the waste meet the definition of solid and hazardous waste?
Is the waste excluded?
Is the waste listed?
Does the waste exhibit a characteristic of hazardous waste?
Hazardous Waste Determination
• Is the waste a solid waste?
• Is the solid waste excluded from the RCRA regulations?
• If the solid waste is not excluded from the hazardous waste regulations, is it a listed
waste? By definition, listed wastes are hazardous wastes.
• If neither excluded nor listed, does this solid waste exhibit any of the characteristics of
hazardous waste? If so, it is a hazardous waste.
Note: Solid waste is determined to be hazardous waste by:
The generator's reasonable knowledge of the characteristics of the waste, or
The generator's testing of the waste.
Listed hazardous waste is hazardous regardless of analyte concentrations in TCLP
extract
1-10
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1.3 THE TOXICITY CHARACTERISTIC RULE
1.3.1 EP Tox Test
What is the Extraction Procedure Toxicity (EP Tox) Test?
What is the EP Tox Test based on?
Landfill leaching,
14 metals and organics form the basis of the EP Tox Test.
Contaminant levels of the EP Tox Test
Relationship to drinking water standards,
.Dilution attenuation factor (DAF).
EP Tox Test was utilized prior to TCLP to ascertain if a waste exhibited the
characteristic of toxicity. The EP Tox Test analyzed waste extracts for 14 specified
chemical constituents.
EP Tox Test was based on the assumption that chemicals placed in a landfill will
leach at a uniform rate into the ground water.
EP Tox regulatory action levels are based upon drinking water standards:
(allowable drinking water level) X 100 = EP Tox regulatory level (assumes that
toxic chemicals leaching out of landfill will be diluted by a factor of 100);
The factor of 100 is termed a dilution attenuation factor (DAF).
The 14 metals and organic chemicals regulated by the drinking water program
were assigned EP Tox regulatory levels.
8 metals
4 insecticides
2 herbicides
Arsenic
Barium
Cadmium
Chromium
Lead
Mercury
Selenium
Silver
Endrin
LJndane
Methoxychlor
Toxaphene
2,4-D
2,4,5 - TP (silvex)
1-11
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1.3.2 TCLPTest
Why replace the EP Tox Test with the TC Rule?
How is TC different than EP Tox?
How regulatory limits are determined for the TC Rule.
Regulatory level = CTRL X DAF
The EP Tox Test was replaced by the TC Rule because of a Congressional
mandate for aggressive regulation of additional toxic constituents.
The original EP Tox Test was not capable of leaching volatile organic
compounds without unacceptable losses during the leach test.
Major changes:
25 additional organic chemicals
different leaching medium
procedural modifications for leaching volatile compounds
The regulatory limit for the TCLP constituents was determined by multiplying
the Chronic Toxicity Reference Level (CTRL) times the Dilution Attenuation
Factor (DAF):
Regulatory limit = CTRL X DAF
The CTRL is a level below which health effects are not expected to occur. The
CTRL is based on: drinking water standards maximum contaminant level
(MCL); or for carcinogens, the risk specific dose (RSD); or for non-
carcinogens, the reference dose (RfD).
1-12
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TABLE 1-1 - TC RULE CONSTITUENTS
EPA WASTE
NUMBER
DOM
D005
O006
D007
D008
0009
D010
D011
D012
001 3
D014
D015
D016
D017
HAZARDOUS
CONSTITUENT1
Arsenic
Barium
Cadmium
Chromium
Lead
Mercury
Selenium
Silver
Endrin
Undane
Metnoxychlor
Toxapnene
Z4-D
Z4.5-TP (Silvex)
Level
(mg/l)
5.0
100.0
1.0
5.0
5.0
02
1.0
5.0
0.02
0.4
10.0
0.5
10.0
1.0
EPA WASTE
NUMBER
D018 ;
D019
D020
D021
0022
D023
O024
O025
O026
D027
D028
O029
DC30
HAZARDOUS
CONSTITUENT2
Benzene
Carbon tetracrdoride
Cnlordane
Chlorobenzene
Chloroform
o-Cresol
m-Cresol
p-Cresol
Cresol (total)
: T;'4r achtorobenzene
1,2-Dtantoroemane
t.i-Dtenioroemyjene
2.4-Dtnitrotoiuene
Level
(mg/l)
0-5
OS :
0.03
100.0
6.0
200.0
200.0
200.0
200.0
7JS
0.5
0.7
0.13 '
EPA WASTE
NUMBER
D031
. D032
D033
D034
0035
DOSE
D037
D038
D039
0040
D041
D042
D043
HAZARDOUS
CONSTITUENT2
Heptachtor (4
epoxWe)
/HexacMorobenzene:: . •
•Hexacrdoro-1.3-
'butddiene
. Hexachloroethane
Metfiylethylketone
Nitrobenzene
Pentachloropnenoi •
Pyridine
Tetrachloroethylene
Trichloroeuiytene
2.3,5-Tiiehk>ioprienoi
2,4.6-TricWofophenol .
vinyl cwortde
Level
(mg/i)
0.008
0.13
as
: . 3J>
200.0
zo
100.0
5.0
0.7
"•5.
400.0
ZO
0.2
1 Original EP Tax constituents.
2 Chemical constituent added by TC Rule (shaded areas).
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1.3.3 TC Rule's Effect Upon Generators and TSDFs
• Generators
Notification
Manifests
Annual report
LDR
• In addition to the above requirements, TSDFs must
Obtain a new permit
Modify an existing permit
Close prior to obtaining a permit
Obtain interim status
Make changes to interim status
Meet minimum technology requirements for pretreatment
Generators which produce newly regulated TC hazardous waste not previously
regulated, must submit notification, use manifests, etc., as required by their generator
status. Generator responsibilities are discussed in Section 1.2.2. If the waste was
previously regulated under EP Tox, no additional requirements are applicable.
Options for TSDFs
Obtain a new permit
Land disposal facilities newly regulated by the TC Rule are required to
comply with minimum technology requirements when new units are
added, existing units are replaced, or existing units are laterally
expanded.
New permit requirements are enumerated in 40 CFR 270.
Modify an existing permit (see Table 1-2)
The three classes of permit modifications are based on the significance
of the modification. This three-tiered process, which replaces the two-
tiered major/minor process, is used by the permittee to initiate a permit
change. In contrast, EPA uses the old major/minor process if it
initiates a permit change.
Class 1 - modifications for routine changes;
Class 2 - modifications for changes of moderate complexity that allow
the facility to respond to changing conditions; and
Class 3 - modifications for substantial facility alterations.
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If waste at a permitted Subtitle C facility exhibits the TC for constituents that
were previously identified as EP toxic, the facility continues to comply with its
permit. No permit modification is needed.
Permitted Subtitle C facilities/units handling newly regulated TC wastes must
submit permit modifications to incorporate:
new TC Rule wastes
new regulated units managing TC Rule wastes
TSDF Options
Close the facility prior to obtaining a permit.
Obtain interim status by submitting a Part A application as an interim permitted
TSDF.
Changes to interim status
Change the conditions of the Part A interim status permit application to
reflect the new hazardous waste.
EPA's new procedures for interim status are listed in
40CFR270.72(a)(1)
No prior approval is required for adding newly regulated units to Part A
permit applications if:
Units were managing new wastes (e.g., TC wastes) on or before
effective date.
Amended Part A was submitted by effective date.
Prior to March 7,1989, new units received approval from EPA.
These new units are not subject to the reconstruction limit,
which restricts cumulative interim status facility changes to less
than 50% of the capital costs of a comparable new facility.
Changes to interim status - Facilities with Surface Impoundments
Implementation of the TC Rule may cause some facilities to alter their
management practices to avoid regulation of certain units under Subtitle
C of RCRA. /
Retrofitting surface impoundments to accept TC wastes entails adding
liners and leachate collection systems not installed when the
impoundment was constructed.
Changes to interim status - Land Disposal Units
New land disposal units should have submitted certification of
compliance with ground water monitoring and financial responsibility
requirements by September 25, 1991.
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Land Ban Requirements
Land disposal restrictions refer to restrictions on the land
disposal of hazardous wastes. Restricted wastes must be
treated as specified in the LOR regulations, otherwise they are
banned from disposal on land.
Any 1C Rule wastes regulated by the LOR regulations would be
prohibited from land disposal.
Minimum Technology Requirements - Surface Impoundments
Surface impoundments which were newly regulated as a result of the
TC Rule were required to meet minimum technology standards by
March 29, 1994.
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Type of Unit
Involved
TABLE 1-2, PERMIT MODIFICATIONS
Permit Change Needed
Modification
Class
Tank or Container
Surface
Impoundment,
Landfill, Waste
Pile, or Land
Treatment
Incinerator
Addition of waste codes or units that will not
require additional or different management
practices than specified in the permit.
Addition of waste codes or units that will
require additional or different management
practices than specified in the permit.
Addition of waste codes or units that will not
require additional or different management
practices than specified in the permit.
Addition of waste codes or units that will
require additional or different management
practices than specified in the permit.
• * s - • •
Addition of units.
If waste does not contain a principal organic
hazardous constituent (POHG) that is more
difficult to incinerate and no additional
performance standards are needed.
If waste contains POHC that is more difficult
to incinerate.
If different performance standards are
needed in the permit.
3
2
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1.4 TC RULE'S EFFECT ON INDIVIDUAL RCRA REGULATIONS
1.4.1 General
The TC Rule has potential impact on other parts of the RCRA program.
Regulations not impacted
Regulations which are impacted
The TC Rule will not affect wastes already considered hazardous. The following
RCRA regulations are not affected by the TC Rule:
Listed hazardous wastes (i.e., the F, K, P, and U lists)
Wastes that are hazardous by the "Mixture" and "Derived From" rules
Wastes already excluded from regulation
The implementation of the TC Rule increases the categories and volume of solid
waste classified as hazardous waste. The expanded definition causes additional solid
waste to be classified as hazardous wastes. The following RCRA regulations are
affected by the TC Rule:
Corrective action and closure
Land disposal restriction (LOR) regulations
Minimum technology requirements for surface impoundments and landfills
Mixture rule exemptions
Previously delisted wastes
Special waste exclusions
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1.4.2 Corrective Action and Closure
1C increased the universe of regulated facilities.
Number of Subtitle C permitted and interim status facilities subject to
corrective action increased.
Number of regulated units within permitted or interim status
facilities undergoing closure increased.
Excavated material from corrective action and closure that exhibits the TC
must be managed as hazardous waste.
TC levels are not used to set clean-up levels for corrective actions or clean
closures.
The TC Rule added more wastes of concern and brought more facilities under the
RCRA program as hazardous waste management facilities. Therefore, additional
facilities are newly subject to the Subtitle C corrective action and closure
requirements.
Previously unregulated TSDFs managing TC Rule wastes were subject to
RCRA requirements if they did not close or change management practices
(e.g., exempt tanks) before the TC Rule became effective.
Existing RCRA facilities may have to amend their closure plans to reflect newly
regulated units as the TC Rule expands the number of regulated units.
Excavated materials, which did not previously exhibit the toxicity characteristic, may
now have to be managed as hazardous waste because of the addition of newly added
constituents to the regulated list.
The Subtitle C corrective action program addresses remediation of hazardous waste
releases from facilities subject to RCRA permitting. The TC Rule levels are neither
action levels nor cleanup standards, both of which are developed from site-specific
information gathered during the investigatory and evaluation phases of the
remediation process.
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1.4.3 Land Disposal Restrictions (LDR)
LOR standards will continue to affect the 14 wastes previously regulated
under the EP Tox Test.
No LDR standards are currently promulgated for the 25 new TC
constituents.
LOR treatment standards are based on the best demonstrated available
technology (BOAT) standards. The characteristic (regulatory) levels were
developed using a risk-based approach.
For some constituents, LOR treatment standards are set at the regulatory
level.
HSWA requires EPA to make an LDR determination for all newly listed wastes within
six months of publication in the Federal Register, or by the effective date of the TC
Rule ruling. Newly listed or identified wastes were not automatically prohibited from
land disposal under LDRs if EPA failed to make this determination within six months
(i.e., no 'hammer" provisions).
EPA set LDR standards for the 14 original EP characteristic constituents, which
EPA does not consider newly identified. These 14 constituents had to meet
LDR treatment standards before land disposal on the effective date of the TC
Rule.
The 25 additional organics identified by the TC Rule are considered newly
identified, and as such have not yet been affected by LDR regulations.
EPA is reviewing the treatability of each TC Rule constituent independently to
determine LDR treatment standards for TC Rule wastes. These standards may differ
from standards set for spent solvent wastes (F001-F005) based on differences in
treatability.
LDR treatment standards are based entirely on technology-based standards
expressed as BOAT. While TC Rule levels are based upon health-based allowable
concentration levels and dilution/attenuation factors, they are not the same as LDR
treatment standards. However, for many TC wastes, EPA has set the LDR treatment
standards at the regulatory level.
This issue is being litigated. Therefore, the LDR treatment standards for TC Rule
wastes may change.
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1.4.4 Minimum Technology Requirements for Landfills and Surface Impoundments
Landfills and surface impoundments newly regulated under RCRA because
of the TC need to comply with minimum technology requirements
HSWA requires that:
Interim status waste piles, landfills, and surface impoundments
must meet certain minimum technology requirements
Surface impoundments must be retrofitted to meet minimum
technology requirements
Existing land disposal units, except surface impoundments, that already contained TC
Rule wastes will not require retrofitting unless they are expanding, replacing units or
continuing to place TC Rule wastes in these units.
The minimum technology requirements (liners and leachate collection systems) for
interim status surface impoundments are found in 40 CFR 265.221.
Surface impoundments that become regulated under Subtitle C because of the TC
Rule must have met the minimum technology requirements by March 29, 1994. This
extension applied to those impoundments that contain the newly identified or
characteristic wastes.
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1.4.5 Exemption for Tanks (Minimum Technology Requirements)
TC wastes treated in wastewater treatment tanks are exempt from
hazardous waste management standards under 40 CFR 264. l(g) and
265.1(C).
Generators that manage TC wastewaters in on-site surface impoundments
may switch to exempt tanks in order to avoid Subtitle C requirements.
However, generators and handlers should have converted their surface
impoundments to tanks prior to effective date of the final rule to maintain
the exemption.
Facilities managing TC wastes after the effective date, even unintentionally,
are subject to interim status requirements.
40 CFR 264.1 (g) and 265.1 (c) exempt wastewater treatment units containing
hazardous waste from Subtitle C regulation.
Generators that continue managing wastewaters in on-site surface impoundments or
non-wastewaters on site will require either interim status or a RCRA permit
modification/change during interim status, depending on whether the facility is
currently a Subtitle C TSDF.
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1.4.6 Mixture Rule Exemption
The mixture rule exemption was not modified by the TC rule; mixtures of
wastewaters and certain listed spent solvents are exempt from Subtitle C
regulations unless the wastewaters:
Exhibit hazardous waste characteristic; or
Contain listed hazardous wastes not specified in the exemption.
TC Rule may regulate currently exempted wastewaters under Subtitle C.
The mixture rule under 40 CFR 261.3(a)(2)(iv) provides an exemption from RCRA
Subtitle C requirements for mixtures of wastewaters and certain listed spent solvents
in low concentrations.
The mixture rule exemption only addresses hazardous waste listings. Therefore, the
mixture rule exemption does not affect the TC Rule.
The mixture rule exemption precludes mixtures of wastewaters and specific listed
spent solvents from hazardous waste regulations, unless they exhibit a characteristic
of hazardous waste.
EPA proposed modifying the mixture rule exemption to make it more consistent with
current risk information.
The TC Rule regulatory levels are based on state-of-the-art toxicological data and risk
assessment methodologies. In contrast, the mixture rule exemption levels are based
upon less current risk information.
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1.4.7 Previously Delisted Wastes
A waste previously "excluded" under Subtitle C regulation may no longer
be delisted if it exhibits a hazardous characteristic (e.g., the characteristic
of toxicity).
TC rule applies to already delisted wastes that now exhibit TC
characteristics.
These wastes are no longer considered "not hazardous"
These wastes must now be managed under Subtitle C
Because delisting levels are generally more stringent than the final TC
levels, the impact of TC rule on previously delisted wastes is expected to
be minimal.
Wastes 'excluded" from Subtitle C regulation under the delisting program may
nevertheless be hazardous if they exhibit a hazardous characteristic (see 40 CFR
260.22). Hazardous waste characteristic levels are those above which a waste is
hazardous due to a particular property; delisting levels are those below which a waste
is not hazardous for any reason. Thus, it is reasonable that these two levels do not
coincide.
Although the TC Rule applies to delisted wastes, EPA does not, in general, expect
that such wastes will become hazardous because of application of the revised TC
Rule. However, if a previously delisted waste exhibits the TC Rule, it will again be
subject to Subtitle C requirements, and the facility will have to notify EPA of its activity.
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1.4.8 Special Waste Exemptions
RCRA defines four special waste categories exempted from Subtitle C
regulation:
Mining wastes
Mineral processing wastes
Oil and gas wastes
Domestic sewage
Subtitle C regulations may apply to these special wastes on a case-by-
case basis.
Special waste exclusions are being reevaluated as mandated by
Congress.
If EPA determines that any special waste should be regulated under RCRA Subtitle C,
the Agency will determine the applicability of the TC Rule to such wastes.
After completing the studies required by RCRA Section 8002, EPA may determine that
one or more special wastes should be regulated under RCRA Subtitle C. Such
wastes would then be listed or the generators required to determine whether the
wastes exhibit a hazardous characteristic, including those specified in the TC Rule.
The TC Rule will have no direct effect on the following types of wastes:
Listed hazardous waste.
Wastes classified as hazardous by the 'mixture" and "derived from" rules.
Wastes already excluded from regulation under 40 CFR 261.4
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1.4.9 Listed Hazardous Waste
1C rule has no effect on listings of hazardous waste
Wastes already listed as hazardous are always considered
hazardous, unless they are delisted.
Hazardous waste listings will continue to supplement the revised TC Rule. The TC
Rule revisions do not eliminate any hazardous waste listings.
Listed hazardous wastes continue to be hazardous even if they contain TC Rule
constituents in concentrations below TC regulatory levels.
TC Rule regulatory levels are not designed to identify the full range of wastes that may
be toxic to human beings. Instead, the characteristic levels were established to
protect human health.
Listed wastes that do not exhibit the toxicity characteristic may nevertheless be
hazardous because:
They contain listed hazardous waste constituents; or
They contain hazardous constituents that are not covered by the TC Rule.
Listed wastes frequently contain hazardous constituents other than the ones cited in
Appendix VII of 40 CFR Part 261. These additional hazardous constituents present in
a waste may not be TC Rule constituents. Removing wastes from a hazardous waste
listing without evaluating additional constituents would be inconsistent with the intent
ofRCRA§3001(f).
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1.4.10 "Mixture" and "Derived From" Rules
TC has no .effect on the regulatory status, of waste "mixtures" or "derived
from" wastes:
Mixtures of listed wastes and solid wastes, and residues derived
from listed wastes, are still'hazardous until delisted.
TC alone is not adequate to regulate mixtures and treatment residues.
Problems may result by applying 'mixture' and "derived from' rules.
The "mixture" rule (40;GFR 261.2(a)(2) (iv)) states that any mixture of a listed
hazardous waste and a solid waste is a RCRA hazardous waste.
The 'derived from' rule (40 GFR 261,3(c)) states that any waste derived from the
treatment, storage, or disposal of a listed hazardous waste is hazardous.
The "mixture" and "derived from', rules creates inequities in the classification of certain
dilute wastes. For example, very, low constituent concentrations in listed wastes may
still be considered hazardous even after treatment. .
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1.4.11 Excluded Wastes
TC Rule does not apply to wastes that are already excluded from Subtitle
C regulations under 40 CFR 261.4:
For example, household hazardous waste is excluded from Subtitle
C; it remains excluded after the 1C effective date.
TC Rule does not add any exclusions to the applicability of previously
promulgated hazardous waste characteristics.
Wastes described in 40 CFR 261.4(b) that are already excluded from Subtitle C
regulations will continue to be exempt from regulation as hazardous wastes, even if
they exhibit the TC Rule.
EPA does not at this time intend to expand the list of exemptions under 40 CFR
261.4(b) to include creosote- and pentachlorophenol-treated wood.
Other wastes that are excluded from Subtitle C in 40 CFR 261.4(b) include:
Household hazardous wastes
Certain mining wastes
Certain solid wastes generated from farming or raising animals
Certain wastes generated from the combustion of coal or other fossil fuels
Wastes associated with the production of crude oil and natural gas
Some chromium containing wastes
Solid waste from extraction and processing of ores and minerals
Cement kiln dust wastes
Certain wood products
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1.5 IMPACT OF TC RULE ON OTHER EPA PROGRAMS
1.5.1 Underground Storage Tanks (USTs)
Two programs currently regulate underground storage tanks (USTs).
Subtitle C (tanks containing hazardous wastes) or Subtitle D (tanks
containing non-hazardous solid wastes),
Subtitle I (tanks containing petroleum product or hazardous
substance products).
The TC Rule may increase the number of tanks regulated under
Subtitle C.
Product (petroleum, hazardous substance) that leaks may become a
hazardous waste and may also exhibit 1C.
Petroleum contains several TC constituents. Therefore, it is likely that some
petroleum-contaminated media will exhibit the TC.
The management of any petroleum-contaminated media exhibiting TC would normally
be subject to Subtitle C requirements for hazardous waste management. However,
EPA believes further study of these impacts is necessary before imposing TC
requirements on media and debris contaminated solely by petroleum from USTs.
EPA has insufficient information on the impact of the TC Rule on UST cleanups;
therefore, EPA has deferred a final decision on the application of the TC Rule to media
and debris contaminated with petroleum from USTs exhibiting the D018-D043 waste
characteristics that are subject to the 40 CFR Part 280 requirements.
EPA believes deferral of a final decision concerning the application of the TC Rule to
UST cleanups is necessary. Imposition of the Subtitle C requirements is likely to
significantly delay cleanups and severely discourage the self-monitoring and voluntary
reporting essential to implementing the UST program.
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Subtitle I and Subtitle C potentially overlap if a substance exhibits the 1C
characteristic and the origin of substance is not known.
The contents of a tank determines which regulatory program (i.e., Subtitle
C or Subtitle I) applies:
Subtitle C regulates hazardous wastes
Subtitle I regulates hazardous products and petroleum
Hazardous product that leaks may become hazardous waste.
Petroleum and hazardous product may exhibit the TC but may not be regulated under
Subtitle C.
Corrective action under Subtitle I addresses releases of product.
Old releases of product not subject to Subtitle I may have occurred:
Via inactive tanks
In areas considered as RCRA solid waste management units
If wastes exhibit the TC for D004-D017, RCRA standards may apply to these old
releases.
TC Rule excludes D018-D043 wastes from RCRA regulation if they are covered under
Subtitle I Corrective Action:
Petroleum-contaminated soil and ground water
Petroleum-contaminated debris (tanks)
EPA is studying impacts of Subtitle C regulation on petroleum-contaminated areas.
Note: Petroleum contaminated media from aboveground storage tanks are also
excluded from TCLP testing requirements where a state has an adequate treatment
mechanism in place.
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1.5.2 Comprehensive Environmental Response and Liability Act (CERCLA)
CERCLA response actions must comply with all applicable, or relevant and
appropriate requirements (ARARs), including RCRA regulations.
1C will cause more Superfund wastes to be classified as RCRA
hazardous wastes.
Thus, more Superfund cleanups will be subject to RCRA
regulations.
TC will not, however, affect CERCLA clean-up levels.
Comprehensive Environmental Response, Compensation, and Liability Act (CERCLA
or Superfund) addresses remediation of inactive waste sites.
ARARs are "applicable or relevant and appropriate requirements." CERCLA must
meet other Federal or State environmental requirements whenever they are applicable
or relevant and appropriate to CERCLA actions.
The primary effect of TC Rule on Superfund will be to regulate many organic
constituents found at Superfund sites as RCRA hazardous wastes.
A current problem at many Superfund sites is determining if an organic
constituent is from a listed RCRA hazardous waste.
There is often little evidence about the source of contamination that exists at
Superfund sites to prove a waste is a listed waste. Therefore, a waste may not
be managed under RCRA (but it will be handled in a protective manner
according to risk assessment).
Under the TC regulation, if tetrachloroethylene is found above the TC
regulatory level, the waste is hazardous regardless of its origin.
As in RCRA corrective actions, Superfund response personnel will not use the TC to
determine whether to undertake a clean-up action. The TC will affect decisions
concerning the management of wastes generated during cleanup activities (i.e.,
hazardous wastes generated during cleanup must be managed in accordance with
Subtitle C). For a lower cost Superfund cleanup option, please read the CAMU Rule
discussion in Chapter 2.
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1.5.3 Clean Water Act (CWA)
The CWA regulates discharges of pollutants to surface waters and to
publicly owned treatment works (POTWs).
Regulatory levels of TC are consistent with those of the CWA:
NPDES effluent guidelines
Pretreatment standards
Treated wastewaters that exhibit the TC Rule.
The Clean Water Act (CWA) regulates discharges of hazardous substances to surface
waters through the National Pollutant Discharge Elimination System (NPDES) permit
program, and pretreatment standards for POTWs.
EPA believes TC levels and CWA standards are consistent.
Thus, CWA discharges are exempt from RCRA regulation under 40 CFR Part 261.
Treated wastewaters exhibiting TC are regulated under RCRA unless:
discharged under NPDES permit
treated in POTW
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Objectives of the Clean Water Act
Impact of the Clean Water Act
Objectives of the CWA are:
To restore and maintain the chemical, physical, and biological integrity of the
nation's waters;
To eliminate the discharge of pollutants into surface waters;
To attain water quality that provides for the protection and propagation of fish,
shellfish, and wildlife, and provides for recreation in and on the water.
Impact of the Clean Water Act:
In lieu of retrofitting and obtaining permits for existing surface impoundments
to meet RCRA requirements, hazardous waste management facilities may
utilize tank treatment and storage of hazardous wastewater. NPDES treatment
tanks are exempt from RCRA permitting requirements.
Wastewater treatment facilities using surface impoundments to treat TC waste
may be subject to RCRA regulations.
The Agency expects many owner/operators to replace surface
impoundments with wastewater treatment tanks.
Wastewater treatment tanks are exempt from Subtitle C regulation
under 40 CFR 264.1(g)(6) and 265.1(c).
If a POTW sludge (from wastewater treatment) exhibits TC, the owner/operator
must treat the sludge to remove the characteristic.
Treatment may be through a pre-treatment program (i.e., before POTW
receives discharge); or
After sludge is produced.
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1.5.4 Safe Drinking Water Act (SDWA)
Safe Drinking Water Act (SDWA) establishes maximum levels of
contaminants acceptable in public drinking water supplies.
Maximum Contaminant Levels (MCLs)
Maximum Contaminant Level Goals (MCLGs)
1C fate and transport models assume ingesting contaminated drinking
water, and uses MCLs as the basis for setting regulatory levels for many
TC constituents.
SDWA protects human health from contaminants in drinking water.
The specific objectives are:
To assure that all people served by public water systems be provided with a
high quality water;
To remove contaminants found in water supplies to protect human health; and
To establish programs to protect underground sources of drinking water from
contamination.
SDWA primary drinking water regulations include MCLs for specific contaminants.
Many TC levels are based on SDWA MCLs.
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Underground injection control (UIC) program regulates injection of fluids to
protect underground sources of drinking water (USDWs).
Five classes of wells are regulated under the UIC program:
Class I - municipal or industrial waste discharged beneath
USDWs
Class II - oil and gas production
Class III - mineral recovery
Class IV - hazardous or radioactive waste into or above
USDWs
"Class V - all other wells used for injection of fluids,
including septic tanks and sumps.
Class I wells are often used by generators of hazardous waste or owner/operators of
hazardous waste management facilities to inject hazardous waste below USDWs. The
largest user of hazardous waste Class I wells is the chemical industry. Class I is the
smallest class of wells with 554 reported in 1989. There are no Class I hazardous
wells in Region 2.
Class IV wells are banned with the exception of wells used for remediation of aquifers
contaminated with hazardous wastes (40 CFR 144.13).
The largest group of injection wells is Class V, with approximately 180,000 wells. The
second largest group of wells is the Class II group with approximately 150,000 wells,
followed by Class III wells with about 20,000 wells.
The Agency is enforcing the ban on shallow injection of hazardous wastes. The
Agency is also developing guidance on best management practices to reduce the
amount and toxicity of wastes injected into Class V wells (40 CFR 144.24).
The TC Rule may increase the number of Class I wells accepting TC waste, and bring
newly identified hazardous Class I wells into the Subtitle C program.
Some Class V wells may be illegally accepting hazardous wastes; the number may
increase as a result of the TC Rule.
Class V wells that may receive TC wastes:
Agricultural drainage wells;
Industrial drainage wells;
Experimental technology wells;
Industrial process water and waste disposal wells;
Automobile service station wells; and
Aquifer remediation-related wells.
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Wastes injected into some Class V wells are exempted from regulation as a
hazardous waste. For example: geothermal electric and direct heat re-injection wells,
several of the domestic wastewater disposal wells, most of the mineral and fossil fuel
recovery-related wells, and certain experimental technology wells.
Many of the facilities that operate Class V wells (e.g., auto service stations) also
generate listed hazardous waste, such as solvents. It is possible that some facilities
are not managing their listed wastes properly, and that hazardous wastes are entering
Class V wells. Of course, when hazardous wastes are injected into Class V wells, they
become Class IV wells.
It is unclear at this time what effects 1C will have on the UIC program because the
Class V program is very new.
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1.5.5 Federal Insecticide, Fungicide, and Rodenticide Act (FIFRA)
FIFRA regulates the sale, distribution, and use of all pesticide products
RCRA regulates listed wastes, including pesticide product wastes.
TC Rule:
adds one pesticide to the list of TC constituents; and
regulates more "multiple active ingredient0 formulations.
Other TC constituents may be ingredients in pesticides.
If pesticide wastes exhibit TC, they are subject to Subtitle C regulation
unless'they are exempt
The following pesticide users are exempt from RCRA requirements:
Household pesticide users.
Farmers who triple rinse their containers, dispose of the containers on their
own farm, and follow the pesticide manufacturer's label instruction for disposal.
Small quantity generators following reduced requirements. Many pesticide
users are small quantity generators.
Properly emptied containers may be exempted from further RCRA
requirements under 40 CFR 261.7. Many pesticide containers, therefore, may
not be subject to regulation as hazardous waste.
There is no change in listed pesticide wastes that are either pure, technical grade, or
sole active ingredient product wastes; they will continue to be regulated under Subtitle
C (P and U listings).
The exemption for arsenic-treated wood was not expanded in the TC Rule.
This exemption may be reevaiuated in the future.
Multiple active ingredient products are usually not regulated as RCRA Subtitle C
wastes, but are instead regulated under RCRA Subtitle D or FIFRA.
TC increases the potential for multiple active ingredient product wastes to be
hazardous.
Adding new pesticide constituents to the TC Rule will primarily affect commercial
applicators, such as aerial applicators and pest control operators. If they use large
quantities of multiple active ingredient pesticide products that have not previously
been regulated, such applicators may be newly subject to RCRA Subtitle C
requirements.
Wastes from multiple active ingredient products that do not exhibit a hazardous waste
characteristic will still be regulated under applicable FIFRA and RCRA Subtitle D
requirements.
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1.5.6 Used Oil Recycling Act
Some used oil exhibits TC or ignitability characteristic.
1C will affect used oil that is
used for road oiling;
that is dumped;
disposed in solid waste landfills and incinerators.
1C will not affect used oil that is:
'Managed by do-it-yourselfers (exempt as household hazardous
waste);
Recycled through energy recovery (40 CFR Part 279 regulates this
activity);
Recycled in any other manner (regulated under 40 CFR 279).
Used oil may exhibit the toxicity or ignitability characteristic.
Disposed used oil which exhibits the toxicity characteristic is subject to full RCRA
Subtitle C regulation (40 CFR 279.80).
However, oil that is burned for energy recovery is not regulated as a hazardous waste.
Used oil generated by household do-it-yourselfers is exempt form RCRA under
40 CFR 279.20(a)(1).
Used oil that exhibits one or more of the characteristics of hazardous wastes
but is recycled in some other manner than being burned for energy recovery is
exempt under 261.6(a)(43).
Significant quantities of used oil may exhibit EP toxicity for metals, but little used oil is
currently recognized as EP toxic.
Shifts in used oil management practices may result from the TC Rule. Management
practices may shift away from road oiling, dumping, and disposal in solid waste
facilities to burning as fuel, recycling, and disposal in Subtitle C facilities.
Standards for regulating used oil that is recycled were promulgated in the Federal
Register on September 10,1992 (FR 41566).
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1.5.7 Toxic Substances Control Act (TSCA)
• TSCA addresses manufacturing, processing, and distributing hazardous
substances such as PCBs.
• If TSCA-regulated products become wastes and contain D004-D017, they
become RCRA regulated.
• If Polychlorinated Biphenyls (PCBs) are fully regulated under TSCA, TC
rule exempts those PCB-wastes containing D018-D043 from RCRA
regulations; not all PCB wastes are fully regulated under TSCA (D004-
D017).
• Exempt wastes include PCB-containing dielectric fluids removed from:
Electrical transformers; and
Capacitors.
Toxic Substances Control Act (TSCA) regulates toxic substances and specifically
addresses PCB management and disposal.
Dielectric fluids from electrical transformers, capacitors and associated PCB-
contaminated electrical equipment could exhibit the TC because they may contain
chlorinated benzenes.
These wastes exhibiting TC are exempted from Subtitle C management
standards if they exhibit waste codes D018-D043.
The exemption applies only to certain wastes noted above that are fully
regulated under TSCA, not to all PCB wastes.
PCB wastes exhibiting D004-D017 characteristics (i.e., those hazardous under EP
toxicity) remain regulated under RCRA if they are a D004-D017 waste under TC (i.e.,
contain other constituents).
1-39
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1.6 POLLUTION PREVENTION
Defining pollution prevention.
Pollution prevention as a national priority for managing hazardous waste.
Priorities of pollution prevention:
Source Reduction
Source Reduction exclusions
Implementation.
The Pollution Prevention Act of 1990 encourages waste reduction at the source rather
than the management of waste already produced.
An integraJ component of EPA's RCRA program is pollution prevention through waste
minimization.
Therefore, EPA's encourages hazardous waste source reduction rather than "end-of-
pipe" controls.
EPA has produced industry-specific outreach materials to assist industry in their waste
minimization efforts (source reduction, process modifications, recycling, and the use
of less toxic materials).
Pollution prevention allows industry to:
Reduce costs of raw materials, hazardous waste treatment and disposal;
Minimize regulatory burdens of compliance;
Minimize liability for environmental problems and occupational safety
problems;
Enhance efficiency and product quality.
EPA encourages industries affected by this ruling to consider achieving compliance
through pollution prevention.
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o Source reduction is:
A practice that reduces the amount of any hazardous waste entering a waste
stream or the environment that occurs prior to recycling, treatment, or
disposal;
A practice that reduces hazards to public health and the environment due to
release of hazardous substances, pollutants, or contaminants.
« Source reduction includes:
Equipment/technology modifications;
Process/procedure modifications;
Reformulations/redesign of products;
Substitution of raw materials;
Improvements in housekeeping, maintenance, training.
• Source reduction does not include:
Practices that alter the physical, chemical, biological characteristics or volume
of a hazardous substance, pollutant, or contaminant through process or
activity that, itself, is not integral to and necessary for the production of the
product or service.
• EPA is implementing the strategy by:
Creating incentives for industry;
Building pollution prevention into their decision-making processes;
Making technical information available to help firms reduce waste generation
through the use of:
The Pollution Prevention Information Clearinghouse (PPIC), a
nationwide network of people and resources with direct experience in
waste reduction strategies in many industries (202-260-1023);
The Pollution Prevention Information Exchange System (PPIES), a
computer electronic bulletin board (703-506-1025) which contains a
database of bulletins, programs, contacts, and reports related to
pollution prevention.
Supporting the development of state programs to assist generators in their
waste reduction efforts;
Initiating specific new regulatory requirements for generators to:
Certify on their hazardous waste manifests and annual permit reports
that are reducing the volume or toxicity of their hazardous wastes as
much as possible;
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Describe on their RCRA biennial reports the efforts undertaken during
the year to reduce the volume and toxicity of their hazardous waste and
compare the efforts to those in previous years;
To require waste minimization/pollution prevention in RCRA permits for
TSDFs that generate hazardous waste.
EPA recommends owners/operators implementing waste minimization programs at
the plant level:
Conduct a waste minimization assessment by selecting a few processes or
waste streams for source reduction or recycling. Accurate records on the rate
of generation and the cost of management should be retained;
Identify waste minimization techniques;
Practice inventory management (substitute less toxic source materials);
Modify equipment (upgrading the performance of process equipment, reducing
leaks and malfunctions, installing conditioning or recovery systems);
Initiate production process changes; and
Recycle and reuse.
Contact the Pollution Prevention Office, U.S. EPA, 401 M Street, SW, Washington,
D.C. 20460 to obtain information or to offer suggestions on how the Agency might
facilitate waste reduction efforts.
Role of the TC Rule in the Pollution Prevention strategy:
By subjecting a larger number of toxic compounds to the RCRA regulations, it
increases the costs to generators of managing solid wastes.
In effect, the TC forces waste managers to rethink their solid waste
management practices due to the high cost of compliance with RCRA Subtitle
C requirements.
The TC will alter the management of previously disposed wastes that might
leach toxic contaminants by restricting their management in land-based units
(surface impoundments, waste piles, lagoons, etc.).
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1.7 CONCLUSIONS
The TC Rule expands the definition of hazardous waste.
The TC Rule adds 25 additional organic analytes.
The TC Rule should encourage facilities to utilize less hazardous
chemicals, to avoid the increased disposal costs associated with the TC
Rule.
By expanding the number of tpxicity characteristic constituents from 14 to 39, EPA
has expanded the definition of hazardous waste, and brought more wastes under the
RCRA jurisdiction. This will keep additional wastes within the RCRA 'cradle to grave"
system and: prevent them fromi harmingI'humarii health or the environment.
By adding organics to the EP Tox inpiganics, the TC Rule addresses the potential
harm these substances could cause in the^environment.
By increasing the costs of disposal for facilities which are now handling hazardous
wastes which were formerly not regulated, facilities are encouraged to find substitutes
or otherwise avoid chemicals which are hazardous.
1-43
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o
tt
TS
«•+
CD
—1
ISJ
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Chapter 2
APPLICATIONS OF THE TCLP METHOD
What is TCLP?
When is the Use of TCLP Applicable?
When is the Use of TCLP Inappropriate?
Sampling and Analysis Design
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2.0 APPLICATIONS OF THE TCLP METHOD
Discussions in this chapter include:
What is TCLP?
• When is the use of TCLP applicable?
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2.1 What is TCLP?
An analytical method to simulate leaching through a landfill. The leachate
is analyzed for appropriate analytes.
TCLP is comprised of four fundamental procedures:
- sample preparation for leaching
- sample leaching
- preparation of leachate for analysis
• leachate analysis
The Toxicity Characteristic does not equal TCLP.
The toxicity characteristic leaching procedure is located in:
Test Methods for Evaluating Solid Wastes, SW-846 Method 1311, July 1992.
Appendix I of this document contains the July 1992 version of Method 1311. When
regulations specify the use of TCLP, approval to deviate from the method must be obtained
from the State or EPA Region.
The Toxicity Characteristic (TC) is utilized to determine whether a solid waste is classified as
a hazardous waste because it exhibits the characteristic of toxicity. The TC of a waste
material is established by determining the levels of 8 metals and 31 organic chemicals in the
TCLP extract of the waste. TC utilizes the TCLP method to generate leachate under
controlled conditions. The regulatory levels of TC constituents in the TCLP leachate are listed
in Table 2-1.
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Table 2-1
TOXTC/TY CHARACTERISTIC CONSTITUENTS - ALPHABETICAL
EPA HW1
Number Constituent
0004] Arsenic
0005* Barium
0018 Benzene
«
0005 Cadmium
D019 Carbon tetrachloride
0020 Chlordane
0021 Chlorobenzene
0022 Chloroform
0007* Chromium
D026 ' Cresol
0023 o-Crescl
0024 m-Cresol
0025 p-Cresol
0016* 2,4-0
0027 1,4-Dicr.lcrobenzene
0028 1 ,2-Dicnlcroethane
0029 1.1-Dichloroethyiene
D030% " 2,4-Dinitrotcluene
0012* Endrin
D031 Heptachlor (and its
epoxide)
DC32 Hexachlorobenzene
D033 Hexach!oro-1,3-butadiene
0034 Hexachicroethane
DOCS] Lead
0013] Lindane
DOC9* Mercury
0014* Methoxychlor
0035 Methyl ethyl ketone
0035 Nitrobenzene
0037 Pentachlorcphenol
0038 Pyridine
0010* . Selenium
D011* Sliver
0039 Tetrachloroetriylene
0015* Toxaphene
0040 Trichloroethvjene
0041 2,3,5-7richiorophenol
0042 2,4,6-7richlorophenol
0017.* . . 2,4,5-7? (Sirvex)
0043 Vinyl Chloride
CTRL
Basis
MCL
MCL
MCL
MCL
MCL
RSD
RfD
RSD
MCL
RfD
RfD
RfD
RfD
MCL
MCL
MCL
MCL
RSD
MCL
RSD
RSD
RSD
RSD
MCL
MCL
MCL
MCL
RfD
RfD
RfD
RfD
MCL
MCL
RSD
MCL
MCL
RfD
RSD
MCL
MCL
* 14 original constituents based on drinking water
1 Hazardous waste number
2 ff o-, m-, and p-Cresol concentrations
cannot be
CTRLs DAF
(mg/l) x of 100 =
0.05
1.0
0.005
0.01
0.005
0.0003
1.0
0.06
0.05
2.0
2.0
2.0
2.0
0.1
0.075
0.005
0.007
0.0005
0.0002
0.00008
0.0002
0.005
0.03
0.05
0.004
0.002
0.1
2.0
0.02
1.0
0.04
0.01
0.05
0.007
0.005
0.005
4.0
0.02
0.01
0.002
standards.
differentiated, the total
Regulatory .
Level (mg/i)
5.0
100.0
0.5
1.0
0.5
0.03
100.0
6.0
5.0
200.02
200.02
200.02
200.C2
10.0
•7.5
0.5
0.7
0.13 .
0.02
0.008
0.13
0.5
3.0
5.0
0.4
0.2
10.0
200.0
2.0
100.0
5.03
1.0
5.0
0.7
0.5
0.5
400.0
2.0
1.0
0.2
Cresol
concentration is used. Total Cresoi regulatory level: 200 mg/L
3 tf quantitation limit is greater than the
limit becomes regulatory teveL
calculated
regulatory level, quamitation
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2.2 When is the Use of TCLP Applicable?
The most common reasons for performing the TCLP are:
• Determining if an unknown waste is hazardous according to 40 CFR
261.24.
• Determining what type of disposal (hazardous waste or solid waste) is
appropriate. Solid wastes are not necessarily Hazardous.
• Demonstrating the effectiveness of treatment processes to comply with
Land Disposal Restrictions (LDR) or "Land Ban" requirements.
Fulfilling shipping or transportation requirements.
Determining if a Waste is Hazardous
The toxicity characteristic regulations require generators to determine whether a solid waste is
a regulated hazardous waste. Generators of potentially hazardous waste can determine if a
waste is hazardous by one of the following methods:
• If a waste is excluded from regulation (40 CFR 261.4), no further determination is
necessary.
• If the waste is listed per 40 CFR 261.30-261.35. Listings may be industry and
process-specific (K-wastes) or may encompass all wastes from non-specific processes
(F-wastes). Listings also include commercial chemical and off-specification products
(P and U wastes).
• If a waste is not excluded or not listed as a hazardous waste, the generator must
ascertain whether the waste exhibits any hazardous waste characteristic: toxicity,
ignrtability, corrosivrty, or reactivity.
• A solid waste is classified as a hazardous waste because of characteristics,
knowledge, or testing.
• If the waste is not listed, and there is not enough information to determine whether the
Toxic Characteristic constituents are present above regulatory action levels, the TCLP
test must be performed.
• The waste generator must certify in writing that the waste is not hazardous and must
maintain records to demonstrate exclusion from RCRA requirements by knowledge or
testing results.
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Characterizing Waste for Disposal
« The RCRA regulations specify how listed and characteristic hazardous waste must be
treated or disposed.
o Hazardous waste disposal facilities are permitted to accept specific categories of
hazardous waste. Hazardous waste disposal facilities cannot accept hazardous waste
without a manifest which lists the constituents or characteristics of the hazardous
waste. TCLP waste characterization may be required by some disposal facilities.
« Disposal facilities may require initial waste testing. After analytical data are collected
from a waste, process knowledge may be used instead of testing.
The Land Disposal- Restrictions (LDR) regulate hazardous waste treatment and subsequent
disposal. The following is a synopsis of the LDR regulations and their CFR citations:
a 40 CFR Part 268 Subpart A
The highlights are:
Definitions of "waste water" (40 CFR 268.2).
Material otherwise prohibited from land disposal may be treated in a surface
impoundment if the residues from that treatment comply with applicable
standards.
Petitions to allow land disposal of 40 CFR Part 268 Subpart C prohibited
wastes must include comprehensive waste and simulation model sampling and
analysis. This typically includes TCLP and other analysis.
Generators of restricted waste must either analyze their waste or its TCLP
extract or use process knowledge to ascertain if the waste complies with 40
CFR Part 268 Subpart D treatment standards for land disposal. The
generators must submit copies of the restricted waste's chemical analysis to
the hazardous waste storage or disposal facility.
Restricted wastes are subject to the treatment standards of 40 CFR Part 268
Subpart D. The generator must notify the disposal company of the restriction
and must supply test data if available.
« 40 CFR Part 268 Subpart B
This section outlines a timetable for waste disposal prohibitions and establishment of
treatment standards.
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40 CFR Part 268 Subpart C
This section outlines waste disposal prohibitions. The following are examples of
hazardous wastes that must meet LDR requirements:
Solvent waste codes F001-F005, including waste from Comprehensive
Environmental Response, Compensation and Liability Act of 1980 (CERCLA)
actions.
Dioxin containing waste codes F020-F023 and F026-F028, including CERCLA
waste.
California List wastes, including hazardous waste that contain 1,000 mg/L
(liquid) or 1,000 mg/kg (non-liquid) of certain halogenated organic
compounds, liquid hazardous wastes that contain _> 50 ppm PCBs, and liquid
hazardous wastes that contain >. 134 mg/L nickel or 2.130 mg/L thallium.
SW-846 Method 9095 must be used to determine if a waste is liquid.
The initial generator of a California List hazardous waste must test the waste
(not an extract), or use knowledge of the waste, to determine if the
concentration levels in the waste meet the regulatory levels for California listed
waste.
Prohibitions for wastes with D, K, P, and U hazardous waste codes are also
listed with effective dates of prohibition.
40 CFR Part 268 Subpart D
This section outlines LOR treatment standards. 40 CFR Subpart D 268.41 lists
treatment standards expressed as concentrations in the waste extract.
A restricted waste may be land disposed only if the TCLP extract of a waste or
waste treatment residue, does not exceed the values shown in Constituent
Concentrations in Waste Extracts (CCWE) of 268.41 for any TC constituent.
Some wastes require total constituent analysis instead of TCLP (see Appendix
The regulation specifies waste/waste residue TCLP extract concentrations
which may not be exceeded. The following Hazardous Waste Codes are
exceptions: D004, D008 (lead), D031, K084, P010, P011, P012, P036, and
U136 (all arsenic), K101 (o-nitroaniline, arsenic, cadmium, lead, and mercury),
and K102 (o-nitrophenol, arsenic, cadmium, lead, and mercury).
The arsenic and lead regulatory levels are based on the EP Tox Test, not
TCLP. If waste/waste residue does not pass the TCLP test, the EP Tox Test
may be used for these contaminants.
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LDR treatment standards are based entirely on technology-based standards
expressed as Best Demonstrated Available Technology (BOAT). 1C levels are
based upon health-based allowable concentration levels and Dilution
Attenuation Factors (DAFs). Therefore, the TC regulatory action levels are NOT
the same as the LDR treatment standards in all cases. For many characteristic
wastes, EPA has set the LDR treatment standards at the characteristic level.
Note that EPA has not yet established LDR standards for D018 through D043
TC wastes.
LDR Records
40 CFR Part 268.7 requires hazardous waste generators and receivers to maintain the
following records of process knowledge or data regarding:
A determination that a restricted waste does not meet treatment standards.
A determination that a restricted waste can be land disposed without further
treatment.
A determination that waste is exempt under 40 CFR Part 268.5, 268.6 or a
nationwide capacity variance under Subpart C of 40 CFR Part 268.
A determination to manage a prohibited waste in tanks or containers during
waste treatment.
The generator must certify that the waste is not hazardous either by knowledge of
testing or by knowledge of process generation. While records are only required for
hazardous waste, it is prudent to maintain records of non-hazardous waste
classification.
The generator must keep records on site for five years from the date that the waste
was last sent to on-site or off-site treatment, storage, or disposal. The record
retention time is extended if an enforcement action occurs within five years of waste
generation.
In general, the types of information required in all of the aforementioned records
include:
Hazardous waste numbers
Manifest numbers
Waste analysis data if applicable
Treatment standards (including codes for required treatment technologies.)
Certification statements signed by the generator
Any waste analysis plans
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LOR Variances: CAMUs are Designed to Reduce the Cost of On-Site Remediation
Corrective action management unit (CAMU) regulations are enumerated in
40CFR260.10 and 40CFR270.2. CAMU is an area within a facility designated
by the Regional Administrator (RA) for implementing CERCLA or RCRA
corrective action requirements. A CAMU may only be used for the
management of remediation wastes pursuant to corrective action requirements
at a facility.
Placement of hazardous remediation waste into a CAMU will not automatically
trigger LDRs. This variance from the LORs can result in substantial cost
reductions. CAMU boundaries are not confined to where contamination exists
at the site; CAMU boundaries are based on where remediation waste will be
managed.
Limitations and Conditions Applicable to CAMU Designations
The CAMU shall facilitate the implementation of reliable, effective, protective,
and cost-effective remedies;
Waste management activities associated with the CAMU shall not create
unacceptable risks to humans or to the environment resulting from exposure to
hazardous wastes or hazardous constituents;
The CAMU may only include uncontaminated areas of the facility if the
incorporated area is more protective than management of such wastes at
contaminated areas of the facility;
Areas within the CAMU, where wastes remain in place after closure of the
CAMU, shall be managed and contained so as to minimize future releases to
the extent practicable;
The CAMU shall expedite the timing of remedial activity implementation, when
appropriate and practicable;
The CAMU shall enable the use, when appropriate, of treatment technologies
(including innovative technologies) to enhance the long-term effectiveness of
remedial actions by reducing the toxicity, mobility, or volume of wastes that will
remain in place after closure of the CAMU; and
The CAMU shall, to the extent practicable, minimize the land area of the facility
upon which wastes will remain in place after closure of the CAMU.
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2.3 When is the Use of TCLP Inappropriate?
• Risk Assessments
The TCLP model assesses risk to ground water when potentially hazardous TC waste
is co-disposed with garbage into sanitary landfills. The TCLP model does not assess
risk when potentially TC waste is disposed in any other matrix. If a waste is
hazardous because it exhibits the toxicity characteristic for mercury, the hazardous
waste generator could attempt stabilization by adding cement and water to the waste,
in a tank, and the resultant concrete may become non-hazardous. In this example,
the concentration of mercury in the concrete's TCLP extract demonstrates that the
waste is not a risk to the ground water beneath a sanitary landfill. Therefore,
according to Federal regulations, this non-hazardous concrete can now be emplaced
at the disposal site: The resultant concrete may only be emplaced on the disposal
site if it does not exhibit the toxicity characteristic for mercury, unless a CAMU is
obtained. The TCLP model discloses no information about potential risks to
groundwater at the factory site where the mercury immobilized in the concrete is
emplaced. EPA is designing site specific risk assessment models, but these will not
be promulgated for several years.
When determining whether to use the TCLP for risk assessment, it is important to
remember that TCLP simulates worst case management of hazardous waste in a
landfill. Much caution must be used before TCLP data are used in risk assessment
because the TCLP conditions rarely reflect actual site conditions. EPA's Science
Advisory Board Report outlines many limitations of using TCLP for risk assessment at
industrial sites. The Board recommends developing leach tests which are appropriate
to site conditions. There are several excellent discussions on the inadequacies of
TCLP organic analysis of solidified waste in "Stabilization and Solidification of
Hazardous, Radioactive, and Mixed Wastes, ASTM, 1992, edited by T. Gilliam and C.
Wiles (Appendix X of this document).
EPA's 1991 Science Advisory Board report on Leachability Phenomena (Appendix VII
of this document) concluded that:
1. Many of the proposed uses of the EP and TCLP test have been inappropriate
because the waste management scenarios of concern were not within the
range of conditions used in the development of the tests themselves. In most
cases of inappropriate use of the EP or TCLP tests, the justification given was
that it was necessary to cite "standard" or "approved" methods. Even if it is
acknowledged that the tests cannot be applied without significant change in
test protocol itself, the need to use a previously "approved" test has been cited
(page 3).
2. A variety of contaminant release tests and test conditions which incorporate
adequate understanding of the important parameters that affect leaching
should be developed and used to assess the potential release of contaminants
from sources of concern. In scientific terms, no "universal" test procedure is
likely to be developed that will always produce credible and relevant data for
input to all decision making exercises (pages 7-8).
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3. Leach test conditions appropriate to the situations being evaluated should be
used for assessing long-term contaminant release potential. The best way to
estimate the extent of contaminant release from a waste matrix of interest is to
have a test that reflects realistic field conditions (page 13).
4. To facilitate the evaluation of risk implications of environmental releases, the
EPA should coordinate the development of leach tests and the development of
models in which the release terms are used (page 17).
The TCLP test cannot predict the potential for toxic chemicals to leach from oily
waste, through soil, to contaminate ground water. This applies to both sanitary
landfills and industrial sites. EPA and the American Society of Testing and Materials
(ASTM) have formed a work group to develop a site-specific risk assessment model
for oily waste. At a minimum, the model will incorporate physical and chemical
characteristics of tine oily waste and the soil. However, this model is not expected to
be approved by EPA for several years. Until EPA approves this site-specific model for
oily waste risk assessments, oily waste site assessments should be based on total
constituent analysis, not TCLP extract analysis.
A percent reduction in organic contaminant concentrations between the original waste
and a TCLP extract of stabilized/solidified waste yields very limited information. In
fact, organic TCLP extract data from stabilized/solidified waste is not realistic because
stabilization/solidification is not an appropriate treatment for organic wastes.
Appendix X lists several papers that describe the problems with measuring organics in
stabilized/solidified wastes. VOA data from stabilized/solidified waste is particularly
ineffectual because concrete curing and concrete particle size reduction (hammering
concrete into small pebbles) both produce heat, which evaporates volatiles from
stabilized/solidified waste. Therefore, all or most of the volatiles will evaporate before
analysis of the stabilized/solidified waste TCLP extract This stabilization/solidification
treatment will therefore appear to be very effective because of analyte evaporation.
The semivolatile organic data in the TCLP extract of stabilized/solidified waste is of
very limited value because the organic compounds are not very soluble in the TCLP
extraction fluid. This usually results in comparable TCLP extract analyte
concentrations between the original waste and the stabilized/solidified waste.
If waste is hazardous because it exhibits the toxicity characteristic for both benzene
and mercury, adding cement and water will bind the mercury, and evaporate the
benzene. At the present time, the LDR regulations do not specify how toxicity
characteristic waste must be treated.
Appendix XV discusses risk assessment for disposal of solidified/stabilized waste and
contaminated soils.
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Unnecessary Hazardous Waste Determinations:
'Generator's knowledge of waste (e.g. chocolate ice cream).
Exempt waste (e.g. household garbage).
Material is not a solid waste (e.g. dean sand, laundry detergent).
Generator's testing of waste (total constituent analysis).
The solid waste is a listed hazardous waste.
,'_ ..)
Unnecessary Land Ban Determinations: :
Some LDRs are for total cbnstituerits, not TCLP extract concentrations.
Generator's testing of waste (total constituent analysis).
Pure liquid waste^samples-(wasteis:TCLP extract; waste would fail paint filter
test). ••-•-.' '.-..>"
Determination of Corrective Action Clean-up Levels and Clean Closures
TC levels are not used to set clean up levels for corrective actions or clean closures.
Glean up levels are developed from stterspecjfic information.
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2.4 Sampling and Analysis Design
The following issues discussed in this section are critical in sampling and analysis
design:
« Total constituents versus TCLP
• Specifying sample collection procedures
Total constituents versus TCLP - EPA Memorandum
EPA has several memoranda which address issues such as Characterizing Heterogeneous
Material and Total Analysis Versus TCLP. These are presented in Appendix VI. The Office of
Solid Waste - Methods Section, Notes on RCRA Methods and QA Activities, Memorandum
#36, January 12, 1993, is helpful in delineating sampling design related to the analysis of
samples for total constituents versus teachable constituents. The consequential portions of
Memorandum #36 and a discussion of their significance follows.
Office of Solid Waste Memorandum - Methods Section #36, January 12, 1993
Page 10 Characterizing Heterogeneous Materials
Characterization of a solid waste is essential for determining whether a waste is
hazardous or for developing management and treatment standards for hazardous
materials. Current EPA regulations for characterizing waste includes determining the
average property of the "universe or whole." This task is difficult when applied to
heterogeneous wastes because conventional sampling and compositing techniques
are often inadequate in providing a "representative sample" of the waste. As a result,
analytical results are often biased and imprecise, making compliance decisions
difficult
The above paragraph means that all of the samples collected from a heterogeneous waste
do not have to be below the regulatory action level for the waste to be considered non-
hazardous. What percent of the samples are allowed to be above regulatory action levels
without classifying the waste as hazardous? Chapter 9 of SW-846 recommends utilizing the
student Y test to determine an appropriate percentage of samples that may be above
regulatory action levels without classifying a solid waste as 'hazardous."
Please be aware that the above discussion is only for heterogenous wastes with no obvious
"hot spots0 of highly concentrated hazardous wastes. Whenever regulatory agencies collect
samples to determine compliance with the TC regulations, only the most contaminated media
will be sampled. For example, if there is a one-acre mercury waste pile surrounded by
ninety-nine acres of clean sand, TC inspectors will not collect samples of the clean sand.
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The RCRA definition of "average property" is very different than the definition of "average"
which was taught in elementary school. For example, if the TCLP extract regulatory action
level is 50 mg/L, and our sample results are 80 mg/L and 0 mg/L, we can not compute the
numerical average of analytical results as 40 mg/L, and affirm that the waste is not
hazardous. To make proper characterization of the above waste, we would declare the waste
hazardous because 50% of the samples were above regulatory action levels. Appendix XI
discusses characterization of heterogeneous waste.
Pages 19-21 Totals Analysis Versus TCLP
Over the past year, the Agency has received a number of questions concerning the
issue of total constituent analysis with respect to the TCLP. Section 1.2 of the TCLP
allows for a compositional (total) analysis in lieu of the TCLP when the constituent of
concern is absent from the waste, or if present, is at such a low concentration that the
appropriate regulatory level could not be exceeded. A number of persons have
contacted the MICE Service and have requested clarification on this issue with
respect to a number of waste testing scenarios.
Wastes that contain less than 0.5% dry solids do not require extraction. The waste,
after filtration, is defined as the TCLP extract The filtered extract is then analyzed and
the resulting concentrations are compared directly to the appropriate regulatory
concentration.
For wastes that are 100% solid as defined by the TCLP, the maximum theoretical
leachate concentration can be calculated by dividing the total concentration of the
constituent by 20. The dilution factor of 20 reflects the liquid to solid ratio employed in
the extraction procedure. This value then can be compared to the appropriate
regulatory concentration. If this value is below the regulatory concentration, the TCLP
need not be performed. If the value is above the regulatory concentration, the waste
may then be subjected to the TCLP to determine its regulatory status.
The same principal applies to wastes that are less than 100% solid (i.e., wastes that
have filterable liquid). In this case however, both the liquid and solid portion of the
waste are analyzed for total constituency and the results are combined to determine
the maximum teachable concentration of the waste. The following equation may be
used to calculate this value:
[AxB + [CxDJ]
B + [20L/kg x D]
where: A = concentration of the analyte in liquid portion of the sample (mg/L)
B = Volume of the liquid portion of the sample (L)
C = Concentration of analyte in the solid portion of the sample (mg/kg)
D = Weight of the solid portion of the sample (kg)
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£ = Maximum theoretical concentration in leachate (mg/L)
To illustrate this point, the following example is provided:
An analyst wishes to determine if a lead processing sludge could fail the TC for lead.
The sludge is reported to have a low concentration of lead, and the analyst decides to
perform a compositional analysis of the waste instead of the TCLP. A preliminary
percent solids determination as described in the TCLP is performed. The percent
solids is found to be 75%. Thus, for each 100 grams of this waste filtered, 25 grams
of liquid and 75 grams of solid are obtained. It is assumed for the purposes of this
calculation that the density of the filterable liquid is equal to one. The liquid and solid
portion of the sample are then analyzed for total lead. The following data are
generated:
Percent solids = 75%
Concentration of lead in the liquid phase = 0.023 mg/L
Volume of filtered liquid = 0.025 L
Concentration of lead in the solid phase = 85 mg/kg (wet weight)
Weight of the solid phase = 0.075kg.
The calculated concentration is as follows:
fO.023 ma/L x .025L1 + f85'ma/ka x .075kaJ = 4.18 mg/L
.025 L + [20 L/kg x .075kg]
In this case, the maximum teachable concentration is below the 5 mg/L regulatory
concentration for lead, and the TCLP need not be performed.
Non-aqueous based wastes (i.e., oily waste) may be calculated in the same manner
as described above, except the concentration of constituents from the liquid portion of
the waste (A in the above formula) are expressed in mg/kg units. Volumes also would
be converted to weight units (kg). The final leachate concentration is expressed in
mg/kg unit
This memorandum should significantly reduce the number of TCLP samples analyzed to
demonstrate compliance with the TC regulations. The profound regulatory impact of Notes
on RCRA Methods and QA Activities Memorandum #36, pages 19-21, are most easily
comprehended with the following uncomplicated monophasic examples. These examples
explain how the calculations are made and evaluated to determine whether to analyze the
total constituents or perform the TCLP.
Example 1. The TCLP Extract Regulatory Action Level for cadmium is 1 mg/L A soil (with
no liquid phase) contains 10 mg/kg of cadmium. Is the TCLP required?
The TCLP test for a solid matrix leaches one part of waste with twenty parts of an acetic acid
buffer. Therefore, even if all of the cadmium was leached from the soil to the solvent, the
maximum concentration in the TCLP extract would be 0.5 mg/L Consequently, TCLP is not
required.
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Example 2. The TCLP Extract Regulatory Action Level for cadmium is 1 mg/kg. A soil (with
no liquid phase) contains 100 mg/kg of cadmium. Is the TCLP required?
The TCLP test for a solid matrix leaches one part of waste with twenty parts of acetic acid
buffer. Therefore, if all of the cadmium was leached from the soil to the solvent, the
maximum concentration in the TCLP extract would be 5 mg/L Consequently, TCLP is
required.
Example 3. The TCLP Extract Regulatory Action Level for cadmium is 1 mg/L A liquid with
no solid phase contains 0.5 mg/L cadmium. Is the TCLP required?
The TCLP test for a liquid with no solid phase consists of filtration. The filtrate is the TCLP
extract. Therefore, even if all of the cadmium passed through the filter, the maximum
concentration of cadmium in the TCLP extract would 0.5 mg/L Consequently, TCLP
extraction is not required.
Example 4. The TCLP Extract Regulatory Action Level for cadmium is 1 mg/L. A liquid (with
no solid phase) contains 5 mg/L cadmium. Is the TCLP extraction required?
The TCLP test for a liquid with no solid phase consists of filtration. The filtrate is the TCLP
extract. Therefore, if all of the cadmium passed through the filter, the maximum
concentration of cadmium in the TCLP extract would be 5 mg/L Since the filtrate equals the
TCLP extract, the waste exceeds the TC level for cadmium and is a hazardous waste.
Therefore, the TCLP extraction is not required.
The following abstract and introduction of a research paper on the relationship between total
mercury and TCLP mercury at Oak Ridge National Lab illustrates how difficult it is to estimate
the mercury concentration in the TCLP extract from the mercury concentration in the soil.
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HAZARDOUS WASTE & HAZARDOUS MATERIALS
Volume 9. Number 3. 1992
Mary Ann Liebert, Inc., Publisher;
Effect of Chemical Form of Mercury
on the Performance of Dosed Soils
in Standard Leaching Protocols: EP and TCLP
K.L. WILLETT
Department of Chemistry. University of North Carolina.
Chapel Hill. NC 27514
R.R. TURNER
Environmental Sciences Division, Oak Ridge National Laboratory,
Oak Ridge. IN 37831
J.J. BEAUCHAMP
Engineering Physics and Mathematics Division. Oak Ridge National Laboratory,
Oak Ridge, IX 37831
ABSTRACT
Application of the EP (Extraction Procedure) and TCLP (Toxicity Characteristic
Leaching Procedure) to a variety of mercury-contaminated soils and solid wastes from U.S.
Department of Energy facilities in Oak Ridge, Tennessee, has not shown any consistent
relationship between test results and total mercury concentrations. To determine the effects of
the chemical form of mercury on leaching results, samples of uncontaminated sofl were dosed
with four different forms of mercury (Hg°, HgS, HgO, Hg2O) at three concentrations (100,1000,
10000 Mg/g) and then subjected to headspace mercury vapor analysis and application of the two
leaching protocols. None of the leaching protocol results for soil dosed with Hg° or HgS
exceeded the Resource Conservation and Recovery Act (RCRA) limit (200 Mg/L) even at the
highest dosing level (10000 Mg/g)- For both mercury oxide forms only the higher soil
concentrations .(1000 and 10000 pg/g) yielded leachate concentrations exceeding the RCRA
limit. In general, the TCLP yielded higher leachate concentrations of mercury than the EP.
This study verified that, where the chemical form of mercury is unknown, total mercury
concentrations in the soil or waste provide no clue as to the performance of a sofl in the
leaching protocols. Results of sample headspace analysis, in addition to TCLP results and
analysis for total mercury, are recommended to fully evaluate the hazards of mercury-
contaminated waste and sofl.
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INTRODUCTION
There are few regulatory and/or advisory criteria for mercury in contaminated soils,
sediment, and waste. Typically, action or clean-up guidelines are developed on a case-by-case
basis. The most widely applied criterion for mercury in solid material is the performance of
solid samples analyzed with the U. S. Environmental Protection Agency Extraction Procedure
(commonly referred to as the EP, reference 1), or (since September 25 1990, reference 2) the
Tenacity Characteristic Leaching Procedure (TCLP). These protocols have been used to classify
wastes under the Resource Conservation and Recovery Act (RCRA). EP or TCLP results,
expressed as the concentration of mercury in the laboratory-generated leachate, are compared
to 200 Mg/L- Results above this criterion are classified as having failed the "toxicity
characteristic." The 200 /ig/L limit represents 100 times the Drinking Water Standard and
-requires the sample to contain at least 4 jig/g. The latter value is derived by multiplying the
established limit, 200 jig/L, by the solution-to-solid ratio in the test, 0.02 L/g. Theoretically, any
sample containing total mercury less than 4 jig/g could not fail the EP or TCLP protocols and
be accordingly classified as hazardous under RCRA. Whfle there are some minor differences
between the TCLP and the EP protocols, most notably the composition of the extraction fluid,
the established limit is 200 /ig/L for both protocols. Rarely, if ever, wfll all the mercury in a soil
or waste be completely teachable in a protocol. Therefore, soil containing considerably higher
concentrations of mercury than 4 /ig/g could theoretically pass the EP or TCLP protocols.
Application of the EP to a variety of mercury-contaminated soils and solid wastes from
US. Department of Energy (DOE) facilities in Oak Ridge, Tennessee, has not shown any
consistent relationship between test results and total mercury concentrations (Figure 1). Low
yields of leachable mercury (less than the RCRA Limit of 200 Mg/L) have not been uncommon
for samples containing several thousand parts per million of total mercury and even for samples
exhibiting visible beads of mercury. Conversely, some soils with relatively low concentrations
of total mercury have exhibited high leachabflity of mercury (>200 /ig/L) and been classified as
hazardous under RCRA.
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-1
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Contaminated Soils and Wastes and Mercury Concentration (/ig/L) in Leachates
Generated Using the EP Protocol
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Chapter 3
TC AND TCLP PROJECT PLANNING
Data Quality Objectives
DQO Case Study:
Cadmium Contaminated Fly Ash Waste
Sampling and Analysis Design
Analytical Method Selection
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3.0 TC AND TCLP PROJECT PLANNING
Planning a project prior to sampling and analysis promotes successful
implementation. The conclusion of the planning process should result in an
efficient sampling and analysis design which allows the collection of appropriate
data. The data should promote making a correct decision on the storage,
treatment or disposal of the waste. This chapter provides information in the
following areas which are critical to project planning.
• Data Quality Objectives (DQOs)
• Sampling and analysis design
Sample containers, preservation, and storage
Sample volumes
Sample decontamination
Holding times
Reid QC
Documentation
Barbara Metzger's 1992 speech on Environmental Data Use: "Meeting the Customer's Need",
(Appendix XVI) - illustrates how site-specific Data Quality Objectives (DQOs) are utilized in
environmental projects.
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3.1 Data Quality Objectives
Environmental samples are often collected and analyzed without proper planning.
The data collected may not allow a correct decision to be made.
In response to this problem, EPA has developed a planning process to facilitate
clear definition of the decision to be made and the data required to make these
decisions. This process is the Data Quality Objective (DQO) process. Prior to
initiating sampling, the questions to be answered should be listed, prioritized and
one primary question identified. These should be agreed upon by all parties,
including the regulatory agencies and TSDFs, the site owners and
operators/generators, and the technical staff.
The DQO Process should identify:
What question will the data resolve?
Why is a specific type, quantity and quality of data needed?
How will the customer use the data to make a defensible decision?
How much data are required?
What resources are needed?
The information included in the DQO section describes the following information:
• DQO definition
• DQO Planning Process (DQO-PP) description
Value of DQO-PP
• Example of DQO-PP implementation
The American Society of Testing and Materials (ASTM) Committee D34.02.10 is working with
Quality Assurance Management Staff (QAMS) and the Office of Solid Waste to produce an
ASTM Standard Practice which describes the DQO Planning Process. (DQO-PP). Additional
guidance is available from the Office of Emergency and Remedial Response, US EPA,
Washington, D.C. 20460 in a document titled: "Data Quality Objectives Process for
Superfund, Interim Rnal Guidance, EPA/540/G-93/071, Publication 9355.9-01, September
1993.
Many of the following flow charts, definitions and information are derived from these
documents and from the draft ASTM document.
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DQOs are defined by the ASTM document as:
Qualitative and quantitative statements derived from the DQO-PP describing the problems,
decision rules, and the uncertainty of the decisions stated within the context of the problem.
The DQO Planning Process is:
A Total Quality Management tool developed by the US EPA to facilitate the planning of
environmental data collection activities. The DQO Planning Process asks planners to
focus their efforts by specifying the use of the data (the decision), the decision
criteria, and their tolerance to accept an incorrect decision based on the data.
Incorrect decisions can result from many causes. One cause of making incorrect decisions
is insufficient or inadequate data to address the problem. The DQO-PP provides a method to
allow the decision makers and technical specialists to assure that sufficient data of
appropriate quality is collected at the proper time. In order to make the best decisions, the
chance of making an incorrect decision must be understood. In order to examine the
probability of making an incorrect decision, it must be understood that all measurements
have error. Measurement error results from heterogeneity of the waste, errors in sampling
methods and laboratory error. Measurement error is cumulative. The laboratory error is a
small component in the overall measurement error. Decision makers must understand that
there is a balance between resources and decision error. Decision makers must make
informed decisions as to the cost versus the decision error and ultimately the measurement
error.
The goal of this document is to assist the regulated community comply with the TC and
TCLP Rules in a cost effective manner. Therefore, it is essential for the regulated community
to understand the importance of obtaining the most cost effective sampling and analysis
design which provides the appropriate decision error. If an appropriate sampling and
analysis design is not utilized, the data may not allow a waste generator to accurately
determine if a solid waste is a hazardous waste. The DQO-PP is essential for preparing a
sampling and analysis design which balances the resources with the chance of making an
incorrect decision.
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What is the value of using the DQO-PP?
The DQO-PP:
• Helps users determine the amount, frequency, and quality of data needed.
• Saves resources by making data collection operations more efficient.
• Encourages communication between the data users, technical experts, and decision
makers.
• Helps focus studies by clarifying vague objectives and narrowing the questions to the
essential issues.
• Helps provide a logical process which facilitates documentation.
Additional critical information about the DQO-PP
• A statistical design, which may result from the DQO-PP, allows the uncertainty in the
data and ultimately the decision uncertainty to be quantified. Chapter 9 of SW-846
outlines strategies for statistical design. The statistical design must be carefully
applied to assure that the correct assumptions are made and that the assumptions
address the question(s) related to the objectives.
• The DQO-PP is iterative. Projects should focus on essential questions and take a
phased approach to answering these questions. This allows revaluation of the DQOs
as the data collection is completed. This iteration allows the resources to be
efficiently used.
• The term 'decision maker" used in this document may include owners and managers
of facilities and regulators. Prior to undertaking large projects, the owners and
managers may choose to involve the regulators to assure consensus is reached in the
planning phase.
The following discussion presents summary information about each of the seven steps within
the DQO Planning Process shown in Figure 3-1.
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State the Problem(s)
Identify the Decision(s)
Identify the Inputs to the
Decision
1
Define the Boundaries
Develop the Decision
Rule(s)
I
Specify Limits on
Decision Error
Optimize the Design
The DQO process is iterative. Changes in assumptions
may be made as new information is obtained.
Figure 3-1 - The DQO Process
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The DQO Planning Process has a logical problem solving structure which includes the
following seven steps:
1. State the problem
2. Identify the decision (s)
3. Identify inputs to the decision (s)
4. Define the study boundaries
5. Develop decision rule(s)
6. Specify acceptable limits on decision error
7. Optimize the design
1. State the problem
The essential goal of this step is to focus the decision makers and the technical team on one
or more problems. These problems should be as narrowly stated as possible. For waste
generators, these problems may focus on whether a particular waste is hazardous.
2. Identify the decision
Clear and concise potential decision (s) should be agreed upon by the decision makers and
the technical team. One or more decisions should be presented for each problem.
3. Identify the inputs to the decision
The goal is to list the data which are needed to make the decision. Questions such as
whether metals or organic data must be generated should be addressed. Production or
process data may be required if the task is related to a waste generator. Additionally,
knowledge about the homogeneity of the material to be sampled may need to be
determined. This data should also include any time factors, physical limitations, process
data, and resources which may effect the sampling and analysis. The environmental
characteristics such as analytes, method, and process knowledge required should also be
listed.
4. Define the study boundaries
The boundaries are the limitations on the study. Examples include time and budget
constraints, permit requirements, disposal requirements, and exposure levels. Any
physical boundaries such as drum or container size is considered a spatial boundary.
Sampling depth may be considered a boundary. Any changes in the waste concentration
over time must be considered as a temporal boundary. This step is often performed
simultaneously with the previous step.
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5. Develop decision rule(s)
This is a statement which describes how the data will be summarized, collected, and
compared to the decision. The statement should include actions which will be based on
criteria and conclusions from the sampling and analysis. The statement should be an
"if-.-then..." statement that incorporates the action limits. The statement should include the
parameter to be measured, the mode of comparison (greater than, less than, average, etc.),
action levels and actions to be taken. An example statement: If the average concentration in
drum is greater than 1 mg/L of cadmium, the material will be disposed of as a hazardous
waste.
Instead of statements, a decision logic diagram may be used to present the decisions and
actions, and criteria. When complex decisions are required or when multiple criteria must be
considered, the decision logic diagram is often more easily followed and understood.
6. Specify acceptable limits on decision error
The decision maker should understand that results of all studies have uncertainty and error.
The goal is to quantitate the amount of uncertainty that the decision maker is willing to
accept in making the decision. The key step is to move from a qualitative "feeling" of
uncertainty to a quantitative level of uncertainty. The process for establishing this, in the case
of a hazardous waste determination, includes the following:
i. Identify the consequences of incorrectly deciding the waste is not hazardous.
ii. Identify the consequences of incorrectly deciding the waste is hazardous.
iii. Rank these consequences by severity.
iv. Estimate the health risk and financial risk associated with an incorrect result.
v. Estimate how far below the regulatory limit one wants to be in order to decrease the
consequence of an incorrect decision. Some statistical experience in assessing
decision error and in assessing sampling and analysis design error is needed to make
this assessment.
This information is incorporated into the decision rule. An example decision rule which
incorporates the decision error is:
Three samples per drum are collected and the concentrations from each drum are
averaged. If the within drum average concentration of cadmium is greater than 0.7
mg/L of cadmium, then the material will be disposed of as a hazardous waste.
7. Optimize the design
In order to characterize a site or waste successfully, a sampling and analysis design must be
established. The sampling and analysis design includes development of statistical and
observational design alternatives, and specifies sampling, handling, and analysis methods.
The design indicates the number and locations of samples based on the acceptable decision
error which was agreed on during the DQO development. The most important input from the
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OQO process is the degree of decision error which the decision maker will accept. When
preparing a sampling and analysis design, the time and budgetary constraints should be
evaluated to balance their importance versus the decision error.
The preliminary design may contain the following information:
Spatial areas of interest
Hot spots versus average values of contamination
Particular contaminants of concern
Desired levels of detection
Which matrices will be investigated
Patterns of contamination
Stratification of the contaminants
Contaminant degradation
Temporal considerations (changes of concentration over time)
Quality control samples designed to allow estimation of precision and accuracy, and
background contamination
• Health and safety issues
Designs must be practical and achievable. There is no one correct design but rather an
optimum design which balances resources with the data required to make a decision.
Technical staff must work carefully to present several designs to decision makers along with
the probability of decision error, resources, and benefits of each design.
Other factors used to select the appropriate measurement methods include:
• DQOs,
• required regulatory or risk assessment levels,
• method precision and accuracy, and
• contaminants of interest.
Improved accuracy, precision, and lower detection limits usually result in higher sampling and
analytical costs because larger numbers of samples, improved instrumentation, and more
field/analytical expertise may be required. The improved accuracy may result in decreased
decision error. If matrix specific accuracy and precision data are not available, preliminary
precision and accuracy studies must be performed. These studies should measure total
error from sample heterogeneity, sampling, and analytical methods. Regulatory agencies
may review these studies prior to method approval.
Prior to sampling design implementation, the decision makers must approve the design.
Several designs may be presented to the regulators and decision makers. The level of
uncertainty, advantages and disadvantages, budgetary and time constraints, and other
relevant factors must be presented for each design. This approach allows the decision
makers to properly assess options and to agree upon the best sampling design. Sampling
designs are implemented after approval by the decision makers.
The technical team must continually evaluate the proposed designs with respect to the
DQOs, health and safety criteria, budget and time constraints. If the proposed design does
not meet the criteria, it may be altered. In extreme cases, the DQOs may be unattainable
and must be altered. The DQOs should only be changed after consultation with the decision
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makers and technical team members. The DQOs may need to be Devaluated if a decision
cannot be made.
References for sampling design strategies are:
• U.S. EPA, Test Methods for Evaluating Solid Wastes, SW-846 Third Edition-Chapter 9.
August 1993.
• Characterizing Heterogeneous Materials, July, 1992 (Appendix XII).
Chapter 9 of SW 846 outlines several statistical design approaches. Many other design
strategies exist and may be better suited for the situation at hand. It is wise to examine
many statistical options and methods of evaluating the data during the planning phase.
An example of using the DQO-PP is presented in the following pages. This example
demonstrates how to design a sampling program to determine whether fly ash from a
municipal incinerator is a RCRA hazardous waste. This example is from a draft ASTM
standard practice on the use of DQO-PP in waste management activities. The ASTM
document was the product of a cooperative agreement between ASTM, US EPA Quality
Assurance Management Staff and the Office of Solid Waste. The example was written by the
ASTM D.34.02.10 committee.
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3.2 DQO Case Study: Cadmium Contaminated Fly Ash Waste
Background
A municipal waste incineration facility located in the Midwest routinely removes "fly ash" from
its flue gas scrubber system and disposes of it in a sanitary landfill. Previously, it was
determined that the ash was "non-hazardous" under RCRA regulations. However, the
incinerator has recently begun treating a new waste stream. As a result, a local
environmental public interest group has asked that the ash be retested against RCRA
standards before it is dumped. The group is primarily concerned that the ash could contain
hazardous levels of cadmium from the new waste sources. The facility manager has agreed
to test the ash and decides to employ the Data Quality Objectives process to help guide
decision-making throughout the project.
The Code of Federal Regulations (CFR) Part 261 RCRA toxicity characteristic criteria for
determining if a solid waste is hazardous requires collection of a "representative portion" of
the waste and performance of Toxicity Characteristic Leaching Procedure (TCLP). During this
process, the solid fly ash will be "extracted" or mixed in an acid solution for 18 hours. The
extraction liquid will then be subjected to tests for specific metals.
Since the impact of the new waste stream is not known, a preliminary study was conducted
to determine the variability of the concentration of the contaminants. Random samples were
collected from the first 20 truck loads. Since process knowledge of the waste stream
indicated that cadmium was the only toxicity characteristic (TC) constituent in the waste,
these samples were analyzed individually for cadmium using the TCLP. The results were
expressed as the average concentration along with the standard deviation.
DQO Development
The following is an example of the output from each step in the DQO process.
Assemble the Team -- The Plant Manager assembled a skeletal team consisting of himself
and a representative of the current disposal facility staff. The two of them assembled the
team with the responsibility to deal with this problem.
The decision makers evaluation team will include the incineration plant manager, a
representative of the environmental public interest group, a representative of the community
where the ash is currently being disposed of. The technical staff include a statistician, and a
chemist with sampling experience.
1. State the Problem
The problem is to determine if any loads of fly ash are hazardous for cadmium under the
RCRA TCLP. If so, those loads must be disposed of in a RCRA landfill.
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2. Identify the Decision (s)
i. Decision - Determine whether the concentration of cadmium in the waste fly ash
exceeds the regulatory RCRA standards.
ii. State the Actions That Could Result From the Decision -
a) If the average concentration of cadmium is greater than the action level, then
dispose of the waste fly ash in a RCRA landfill.
b) If the average concentration of cadmium is less than the action level, then
dispose of the waste fly ash in a sanitary landfill.
3. Identify the Inputs Needed for the Decision
List the environmental variables or characteristics which are known from historical and
regulatory information and information which must be obtained in order to make the decision.
Available Inputs
Preliminary Study Information - Since the concern is with a new waste stream, the team
ordered a pilot study of the fly ash to determine the variability in the concentration of
cadmium between loads of fly-ash leaving the facility. They have determined that each load
is fairly homogeneous. However, there is a high variability between loads due to the nature
of the waste-stream. Most of the fly ash produced is not a RCRA hazardous waste and may
be disposed of in a sanitary landfill. Because of this, the company has decided that testing
each individual waste load before it leaves the facility would be the most economical. In that
way, they could send loads of ash that exceeded the regulated cadmium concentrations to
the higher cost RCRA landfills and continue to send the others to the sanitary landfill.
The study showed that the standard deviation of the cadmium concentration within a load
was S,, = 0.4 mg/L and the standard deviation of the cadmium concentration between loads
was Sb = 1.4 mg/L Sample and quality control data indicates that a normal distribution can
be assumed.
Identify Contaminants of Concern, Matrix, and Regulatory Limits - The team identified the
following factors critical to the problem:
• Contaminants of concern: cadmium soluble in the Toxic Characteristic Leaching
Procedure fTCLP) extract.
• Sample Matrix: fly ash.
• Regulatory Threshold: 1 mg/L
Specific Project Budget and Time Constraints - The incinerator plant manager has
requested that all stages of the operation be performed in a manner that minimizes the cost
of sampling, chemical analysis and waste disposal. However, no formal cost constraints
have been implemented.
The environmental public interest group has threatened to file a law suit for violation of
environmental regulations if testing does not proceed within a "reasonable time-frame.'
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Contained in the trucks, the waste does not pose a threat to humans or the environment.
Additionally, since the fly ash is not subject to change, disintegration or alteration, the
chemical properties of the waste do not warrant any temporal constraints. However, in order
to expedite decision making, the evaluation team has placed deadlines on sampling and
reporting. The fly ash waste will be tested within 48 hours of being loaded on to waste
hauling trailers. The analytical results from each sampling round should be completed and
reported within 5 working days of sampling.
Identification of the testing methods - In this case, 40 CFR Part 261, Appendix II specified
the TCLP method SW 846 Method 1311. The leachate must be analyzed by an appropriate
method. Potential methods of characterizing the leachate for cadmium include, but are not
limited to, SW 846 methods 6010, 6020, 7130, or 7131.
Inputs To Be Determined
Method validation and QC - The analytical method accuracy and precision and method
detection limits in the fly ash matrix must be determined. The QC samples must be
specified.
Identification of sampling procedure or devices - The following must determined:
- Number of samples
- Sampling methods for composite or grab samples of ash
- QC requirements for sampling
4. Define the Boundaries of the Study
Define a detailed description of the spatial and temporal boundaries of the decision;
characteristics that define the environmental media, objects or people of interest; and any
practical considerations for the study.
i. Specify the Characteristics that Define the Sample Matrix - The fly ash should not be
mixed with any other constituents except the water used for dust control.
ii. Identify Spatial Boundaries •- The variability between loads was greater than within a
load therefore, decisions will be made on each load. The waste fly ash will be tested
after it has been deposited in the trailer used by the waste hauler. Separate decisions
about the toxicity of the fly ash will be made for each load of ash leaving the
incinerator facility. Each load of ash should fill the waste trailer at least 70%. In cases
where the trailer is filled less than 70%, the trailer must wait on-site until more ash is
produced and can fill the trailer to the appropriate capacity.
iii. Identify Temporal Boundaries (The temporal boundaries of the study include the time
frame over which the study should be conducted). - The study will be conducted until
at least 30 data points are collected and the action limits, number and frequency of
samples will be reevaluated after that time.
5. Develop a Decision Rule
The arithmetic mean of sample results will be compared to the action level.
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Decision Rule:
a) If the average concentration of cadmium in a truck load is greater than the
action level, then dispose of the waste fly ash in a RCRA landfill.
b) If the average concentration of cadmium in a truck load is less than the action
level, then dispose of the waste fly ash in a sanitary landfill.
Note that the team has decided that the action level will be less than the regulatory level in
order to decrease decision error at the regulatory level of 1 mg/L
Develop Decision Error Constraints
The decision makers specify acceptable decision errors based on the consequences of
making an incorrect decision. Both error rates have negative consequences.
The team must make a baseline assumption. Based on the initial pilot study each load will
be assumed to be less than the regulatory level and the burden of proof will be to prove that
the load is above the action level. In this example, there are two types of error that the
evaluation team could make:
i. false positive error (declaring the load hazardous when it is not) - If the true cadmium
concentration is below 1 mg/L, but the average measured cadmium concentration is
above the action level, the non-hazardous fly-ash waste will be sent to a RCRA landfill.
The consequence of a false positive error is that the company will have to pay
additional cost to dispose of the waste with a concentration between the action level
and regulatory threshold at a RCRA facility as opposed to a less expensive method of
disposal in a sanitary landfill.
ii. false negative error (declaring the load non-hazardous when it is hazardous) - If the
true cadmium concentration is equal to or greater than 1 mg/L, but the average
measured cadmium concentration is below the action level, the hazardous fly-ash
waste will be sent to a sanitary landfill. The consequence of a false negative error is
that the fly-ash waste may be disposed in a manner that will be harmful to human
health or the environment. Legal consequences and subsequent remedial costs are
also possible consequences.
iii. number of samples - The number of samples will depend on the uncertainty of
estimating the true cadmium concentration for each load and the resources available
to sample and to chemically analyze the samples.
The purpose of this stage of the process is to specify the probabilities of making an incorrect
decision on either side of the "action level" that are acceptable to decision makers. The team
must agree on which type of decision error is of greater concern, false positives or negatives
and must target the level of false positives and negatives.
For this example, the project team is more concerned about false negatives because of the
increased liability due to sending potentially hazardous waste to a sanitary landfill. The team
set a target level of false negatives of 10% when the true concentration is 1 mg/L
3-13
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Decision Performance Curve
The Decision Performance Curve will be calculated to determine the action level and review
the performance of the decision rule. To calculate the Decision Performance Curve, decision
makers use the following steps:
. Step 1: Number of samples are calculated with L = 0.2 mg/L, o = Sw = 0.4
mg/L, and a = 0.05 (or Z^ = 1.960 for a 95% confidence level).
„ . f
I
uao x 04
0.2
where:
L = the limit of error on the average of 0.2 mg/L
Sw or standard deviation = 0.4 mg/L within a load
Zc/2 = 1.960 for a 95% confidence level, the «/2 percentile point of normal probability
distribution e.g. Z^ = 2^. These are tabled values from a standard normal
distribution at
n = number of samples
Step 2: Calculate the action level (AL) from the specified false negative error of
10%. The probability calculations are based on an approximating
normal probability distribution for the cadmium concentration
measurements. This approximating normal probability has a mean =
RT = 1.0 mg/L and a standard deviation = S^, = 0.4 mg/L The 10%
percentile point for the standardized normal probability distribution is
Zaio = 1-282-
False Negative Error = Pr( Average < AL when the true concentration = RT) =0.10.
or
AL- RT
AL = Action Level
RT = Regulatory Threshold
Zo-,0 = Tabled Z-value from standard normal distribution at 0.10
AL = 1.0/nrfL - (1.282)(0.4mtfL) / 4 = 1.0mfjL - 0.13/rg/L ,
or
3-14
-------
AL = 0.87 mgfL .
Therefore, the decision rule is:
a) If (average concentration of cadmium) ^ 0.87 mg/L then dispose of the
waste fly ash in a RCRA landfill.
b) If (average concentration of cadmium) < 0.87 mg/L, then dispose of
the waste fly ash in a sanitary landfill.
The decision performance curve for this decision rule would have a probability of
taking action (i.e., sending fly-ash waste to a RCRA landfill) of 0.90 at a possible true
concentration value of RT = 1 .0 mg/L
Step 3: Calculate the true concentration (say, 6 < RT) that corresponds to an
action level of AL = 0.87 mg/L and a false positive error of 20%. The
probability calculations are based on an approximating normal
probability distribution for the cadmium concentration measurements.
This approximating normal probability has a mean = 6 mg/L and a
standard deviation = Sw = 0.4 mg/L The 20% percentile point for the
standardized normal probability distribution is Z^ = 0.848.
False Positive Error = 'Pr{ Average < AL when the true concentration = 6} = 0.20.
or
AL = Action Level
6 = True Value
ZO^Q = Tabled Z-value from standard normal distribution at 0.10
6 = 0.87/ntfL - (0.848)(0.4/wc/L) / 4 =
or
6 = Q.79mgfL .
The decision performance curve would have a probability of taking an action (i.e.,
sending fly-ash waste to a RCRA landfill) of 0.20 at a true cadmium concentration of 8
= 0.79 mg/L The possible true cadmium concentration values in the interval (0.79
mg/L, 1 .0 mg/L) represents values that cause the decision rule to send fly-ash waste
to a RCRA landfill even though the true concentration is below the regulatory
threshold. This interval can be reduced by increasing the number of samples, by
changing the false negative error or by changing the false positive error.
3-15
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Step 4: Draw the decision performance curve by using the standardized normal
probability distribution. The standardized normal probability distribution
is defined as a normal probability distribution with mean = 0 and
standard deviation = 1.0. There are many tables and computer
programs that can be used to calculate probabilities for a standardized
normal random variable, Z. A normal random variable, X, with mean =
\i and standard deviation = a can be transformed to a standardized
normal random variable by Z = (X - n)/o.
Prob( Action ) = Pr( Average i AL when the true concentration = 6).
Proti(Action) = 1.0 - Prodz *
v
Pmti(AcSon) = 1.0 - /Wz & a87"9
\ W.I . /
Rgure 3-2 plots the decision performance curve of Prob( Action ) versus possible true
concentration values 6.
7. OPTIMIZE THE DESIGN
The decision maker(s) will select the lowest cost sampling design that is expected to achieve
the DQOs. The optimal design (s) for sampling the fly-ash waste will be generated by the
statisticians on the evaluation team. The choice of sampling plan will be decided by
consensus.
Rgure 3-2 plots the probability of taking action (disposing of the waste in a RCRA landfill)
versus different possible values for the true concentration in the TCLP extract. Note that
various numbers of samples, n, are used to generate each curve. All of the curves meet the
criteria of 10% false negatives at the regulatory threshold. The differences lie in the false
positives versus the true concentration. If the true concentration value is equal to .87 mg/L
(the action level) then the probability of taking action is .5 or 50% chance of taking action.
The action level is below the regulatory threshold and does insure the agreed upon false
negative rate of 10%. Note that if the regulatory level and the action level were equal, the
likely chance of having a false negative would be 50% at 1 mg/L.
3-16
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Cadmium Contaminated Fly-Ash Waste
1.1 1.2
Tnje Cadmium
Concentration (mg/L)
Rgure 3-2. Design Performance Curve for Cadmium Example
Implementation - After completion of the sampling and measurement process, the data
assessment is performed. The concentration measurements from each load of fly-ash waste
are averaged and compared to the action level. Any load with average concentrations less
than the action level will be sent to a sanitary landfill, and those loads with average
concentrations greater or equal to the action level will be sent to a RCRA landfill.
3-17
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3.3 Sampling and Analysis Design
Specifying Sample Collection Procedures
• The methods and equipment used for sampling waste materials vary with the physical
and chemical properties of the waste materials.
• 40 CFR Part 261, Appendix I lists several representative sampling methods.
Unfortunately, for most matrices, selecting representative samples is an extremely
difficult objective.
• The methods in the above reference are recommended. No prior approval by EPA is
required if alternate sampling methods are used.
• All procedures for sampling should be documented and referenced.
Sample Containers, Preservation, and Storage
Prior to Extraction or Filtration
• No preservatives are added to the initial waste collected for TCLP filtration and
extraction.
• Preservatives used after filtration and extraction are listed in Chapter 4 of this
document.
• If organics are being analyzed, samples must be collected in glass containers with
Teflon lid liners.
• Metals may be collected in polyethylene or glass containers.
• If practical, samples which will undergo Zero Headspace Extraction (ZHE) for volatiles
should be collected in 40 ml glass Volatile Organic Analysis (VOA) vials with Teflon
lids. Clay type soil samples, or other large particle size solid matrices which are
difficult to put into narrow-mouth containers, should be collected in 250 ml wide
mouth glass jars.
• Any sample which will undergo ZHE should be collected with minimal head space in
the container.
• All samples should be stored at 4°C +. 2eC prior to extraction or filtration. Samples
should be placed in coolers immediately after collection.
Sample Volumes
A discussion of required sample volume is presented in Chapter 4 which includes the
following general points:
• A minimum of 100g of waste is needed to determine the percentage of solids,
extraction fluid type, and particle size.
3-18
-------
• A second aliquot of 100g is the minimum which must be extracted for non-volatiles.
The amount of sample is dependent on the percent wet solids. The lower the percent
wet solids, the greater the sample volume required for leaching.
• Another aliquot of at least 25g must be used for volatiles by ZHE. The amount of
sample is dependent on the percent wet solids. The lower the percent wet solids, the
more material which must be collected for leaching.
• If multiple phases are collected and the solids appear to be _<0.5%, each phase may
have to be analyzed individually. This is especially true of oily waste. If the oil will not
pass through the filter, it will be considered a solid.
• Enough sample must be collected to allow for the matrix spike. Each matrix requires
a spike. The same amount of material is required for the spike as for the sample.
• Extra sample volume may be needed if vessel leakage or breakage occurs. Multi-
phasic samples require much larger sample volumes than monophasic samples.
Sampling Equipment Decontamination
Acceptable sampling equipment decontamination should be performed before sample
collection. Decontamination may be required in the field if an adequate number of pieces of
sampling equipment is not available to allow equipment to be dedicated to one sampling
point.
Each EPA region and some states have special decontamination requirements. These
decontamination requirements should be verified for compliance in a particular region or
state. The RCRA decontamination procedures may differ from CERCU\ decontamination
procedures in some locations. For most TCLP sampling events, there are no sampling
equipment decontamination criteria.
Paint or coatings on sampling equipment must be removed from any part of the equipment
that may contact the sample.
The USEPA Region 2 decontamination procedure for CERCLA sampling and RCRA Facility
Investigation (RFI) sampling is as follows:
a. wash and scrub with low phosphate detergent
b. tap water rinse
c. rinse with 10% HN03, ultra pure
d. tap water rinse
e. an acetone-only rinse or a methanol followed by hexane rinse (solvents must be
pesticide grade or better)
f. thorough rinse with demonstrated analyte free water*
g. air dry, and
h. wrap in aluminum foil for transport
* The volume of water used during this rinse must be at least five times the volume of
solvent used in Step e.
3-19
-------
If metal samples are not being collected, the nitric acid rinse may be omitted. If organic
samples are not being collected, the solvent rinse may be omitted.
Holding Times for TCLP
• TCLP has three sets of holding times (see Table 3-1). The first holding time
commences with sample collection and ends with TCLP extraction. The second
holding time is from TCLP extraction to preparative extraction. The final holding time
is from preparative extraction to analysis.
Table 3-1 - TCLP Holding Times
Analysis Type
Volatiles
Semivolatiles*
Metals, except
Mercury
Mercury
Days From Field
Collection to TCLP
Extraction
14
14
180
28
Days From TCLP
Extraction to
Preparative
Extraction
NA
7
NA
NA
Days From
Preparative
Extraction to
Determinative
Analysis
14
40
180
28
* Pesticides and herbicides are deemed semh/oiatiles.
• Some regional and state agencies may alter these times. If Contract Laboratory
Program (CLP) methods are used, the holding times from extraction to preparation
and from preparation to determinative analysis will differ from the above times.
However, to demonstrate compliance with the TC or Land Ban regulations, sample
holding times may not exceed the holding times listed in the preceding table.
Field QC Samples
The following field QC samples may be collected during the sampling process:
• Trip Blanks are aliquots of analyte-free water brought to the field in sealed containers
and transported back to the lab with the sample containers. Trip blanks, which are
only analyzed for volatiles, are especially useful when aqueous volatiles are collected.
Trip blanks allow one to assess contamination from transport and storage.
*
• Equipment Blanks are analyte-free water which is poured over the sampling
equipment in the field after the final rinsing of equipment. Equipment blanks allow
one to assess cross contamination and decontamination procedures.
Several key issues must be understood when evaluating the need for equipment
blanks. Equipment blanks are analyzed for total constituents while waste undergoes
extraction. The TCLP leaching process uses 20 grams of leaching fluid per gram of
3-20
-------
wet weight sample. Therefore, TCLP equipment blanks may not be cost effective for
some types of TCLP sampling. However, if sampling is being done for legal
purposes, such as enforcement actions or potential litigation, equipment blanks
should be collected to assure that the data are legally defensible.
• Reid Duplicates are samples collected from the same location and waste source at
the same time. The goal is to determine variability in the waste or sample matrix. The
frequency of these depends on the sampling design. Most agencies recommend at
least 5%. Duplicates provide information about sampling and analysis precision.
• Laboratory Duplicates are samples which have sufficient volume to allow the
laboratory to homogenize the sample, split the sample and prepare and analyze both
aliquots as separate samples. The purpose is to assess precision between two
laboratory analyses on the matrix.
Enough sample volume must be collected for the lab to generate matrix spikes and
laboratory duplicates. The frequency of these samples varies, and depends on the different
types of waste collected, the time over which they are collected, and the regulatory
requirements.
Sampling Documentation
« All sample locations should be identified in a log book. Locations should be from a
surveyed point when applicable. Both horizontal and vertical coordinates should be
documented. Each sampling point should be assigned a unique number or other
identifier.
• Unique sample numbers, collector, date and time of collection, container types, matrix
and analysis required (including TCLP and the extract/filtrate analysis) should be
documented in field log books, chain-of-custody (COC) forms, and on sample labels.
• In most cases, a COC should be used to document the collection and transport of
samples to the laboratory. The chain of custody form should be signed and dated by
individuals who collect, transport or receive the samples. Copies of COCs should be
kept by sending and receiving parties.
• Any deviations from the sampling plan should be documented in the log books.
• The type of sampling equipment utilized must be documented in the log book.
• Ambient weather conditions at the sampling location(s) should be documented in the
log book.
3-21
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3.4 Analytical Method Selection
Strategy for Analytical Method Selection:
• Determine the analytes
• Determine the methods of analysis
• Specify detection limits and regulatory action levels
• Specify quality control samples and requirements
To specify appropriate analytes to demonstrate compliance with the TC regulations, the data
requester needs to understand the basic groupings of analytes which are performed by each
analytical method. The data requester also must understand the typical detection limits and
the issues which revolve around not being able to achieve these limits. The following tables
outline the TC constituent, the category of the analyte, and the potential methods of sample
preparation and analysis. The current CLP contract required detection limtts/quantitation
limits and the SW-846 practical quantrtation limits are also presented in this section.
The analytical method information should be used in conjunction with process knowledge
and Table 3-2, which lists the TC constituents and regulatory levels, to plan the sampling and
analysis.
3-22
-------
TABLE 3-2 - TC ANALYTES AND THEIR REGULATORY LEVELS
Constituent1
.
Arsenic
Rarium
^
Cadmium
Chromium
Lead
Mercury
Selenium
Qjlupr
Endrin
• -i
Lindane
Methoxy-
chlor
Toxaphene
2 A r\
,4-U
2,4,5-TP
(Silvex)
Regulatory
Level
(mg/l)
5r\
.(j
1000
.0
.
5.0
5.0
0.2
1.0
5 0
0.02
OA
,«t
10.0
0.5
1.0
Constituent2
.•._/•::•:•:••: ::::::•..::-.••:..•,:.•••:•:••••:.••:
. BenZene..;-.;;;..;;;,..... ;.;;.;.•
•••Gjarfcjori' ••>••'••• '•'•••••';••'•• •
:tetrachlbnde^:x::::
....."-.v,.-;.,- ..;..-.;..... .••••.... .••:•:•;•.•••:::•:
>Chlprdane: ::..::::
•Chlcroberizene ;
^Chloroform \ S
^f^t-i
CTVCfeSOl:' ••"•"• ;>•
• o-ftresol •••' ..'::•:-.:
.Cres6i:(totaij ;::;:.
•• • •••..-.;.•;.; •,.. . I;-'.;-.;.;.;:;:;.
•*•.:.: , v.1-
•••benzene' :•::,:••••:•••:••••:.•;
Diclhloroethane
1,1-Dichloro^; ::..;
elhylene ::;;...;:;
2 •:*..- ' . .' : •':...
,4-- • • ••• ••.
Diriitrbtbluene . \
Regulatory
Level
(mg/l)
;::•>••••::••: ;:;• ,,-..
••••••••.,:•:,,•-:. ,-.-.CX5:--
I::. .••••;:••:•.• .•./j-e-.j
.v. • • •.•••.• •*?•&••
:•:..•: .0.03
•• •-• -100.0
•>' '• . -: • ' :-'6^0:
.H. 200.0
; • 200-0
: 2000
.;;•:.. -200.0
,.;..- . .-: •: : •••
v." •••.•..•.••
• 0.5
:. . . . OJ
0' io •
: 1 o .
Constituent2
neptacnior •••: .
: H^xachioro-: :::
ncAaUI IIUl.Lr*. .
•benzene... .. :
. • . . •...••.•..-..••.•••.
Hexacnlbro-: ::
•1 '3- ••••:•••• '•..". •"•••
tKl.ff 2k«JJAMA'.V . ' . ."'
uuiduicnc. ...... .
Hexachiorb-
ethane • : : ;
Methyl ethyl;:
fcptnrii ''•'•' '•"•'"•'
Kciune
Nrtrb-..:
:benzene
: Peritachibrb- :
phenol : :
Purirlinp-.- •'.'•
Tetracnloro^: :
ethylehe;: :• .:
...-••. .. . " • :
TrichlorO"
ethyFerie :
2,3,5-
Trichlbro-
-.U-k— lil' •
pnenor • ;•
2,4,6^ .; -:-;;...--;
Trichlorb- ..,: ::
phenol :: •:
vinyi cnionae
Regulatory
Level
(mg/l)
:......: .0.008
•:•••••••:.•••:••••.•• : n -to
•:- "V'."'" '-P-5..
,.---. •••,.••• 3 :Q
•: •:•."•• ..200.0
• 2-°:
;: TOO.O
.-.: . •••: . 5.-0-.
•;•:." • ."''•'•°-7.
•;.: : •
... . . .
;:• 400,0
:::•:•• 2,0
'••• • n:ov
1 Original EP Tox constituents.
2 Chemical constituent added by TC Rule (shaded areas).
3-23
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General Method Information
There are two categories of permissible methods used to analyze TCLP extracts:
1. Many state environmental agencies mandate the use of SW-846 methods for
hazardous waste determinations. SW-846 methods are sometimes also required to
demonstrate compliance with the RCRA regulations. Several different SW-846
methods may be used to analyze 1C analytes. Appendix IX explains when SW-846
methods are mandatory.
2. Any appropriate EPA approved method may be used to demonstrate compliance with
the TC regulations. However, if the data are going to be validated, CLP methods are
recommended. Two semi-volatile TC analytes (m-cresol, pyridine) are not included in
the CLP target compound list of analytes. Therefore, the method must be slightly
modified to incorporate these two compounds.
Specifying detection limits and regulatory action levels
• The method or contract detection limits must be evaluated versus the regulatory TC
limits. The method or contract limits must be lower than the regulatory limits.
• There are three compounds which have quantitation limits that exceed the regulatory
limits: 2,4-dinitrotoluene, hexachlorobenzene, and pyridine. In these cases, the
quantitation limit becomes the regulatory limit.
• The EPA Region 2 TCLP SAS Request (Appendix VIII), shows recommended TC
detection limits which are increased in order to minimize matrix effects.
Metals Analysis Information
• Metals analysis can be performed by three methods: Inductively Coupled Plasma
(ICP), Rame Atomic Absorption (FAA) and Graphite Furnace Atomic Absorption
(GFAA).
Laboratories usually analyze metals, except mercury, in the TCLP extract by
ICP.
Mercury is usually analyzed by Cold Vapor Atomic Absorption (CVAA).
The GFAA generates lower detection limits than ICP method.
• The CLP Contract Required Detection Limits (CRDLs) are the same for both ICP and
GFAA.
3-24
-------
Table 3-3 Metals Analysis Method By ICP
Analyte
Arsenic
Barium
Cadmium
Chromium
Lead
Selenium
Silver
SW846
Preparation/
Analysis
3010/6010
3010/6010
3010/6010
3010/6010
3010/6010
3010/6010
7760 (prep
only)/6010
SW 846 PQL,
mg/L(1)
.05
.002
.004
.007
.04
.07
.007
CLP CRDLs,
mg/L (2)
.01
.2
.005
.01
.003
.005
.01
(1) PQL = Practical Quantitation Limit = EQL = Estimated Quantitation Limit
(2) Contract Laboratory Program, Statement of Work for Inorganic Analysis, ILM03.0
Table 3-4 Metals Analysis Methods by GFAA and Mercury by CVAA
Analyte
Arsenic
Barium
Cadmium
Chromium
Lead
Selenium
Silver
Mercury
SW846
Preparation/
Analysis
7060/7060
3020/7080
3020/7131
3020/7191
3020/7421
7740/7740
7760 (prep
only)/7760
7470
SW 846 PQL,
mg/L(1)
.001
.1
.001
.001
.001
.002
.01
.0002
CLP CRDLs,
mg/L (2)
.01
.2
.005
.01
.003
.005
.01
.0002
(1) POL = Practical Quantitation Limit = EQL = Estimated Quantitation Limit
(2) Contract Laboratory Program, Statement of Work for Inorganic Analysis, ILM03.0
3-25
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Table 3-5 Pesticide and Herbicide Quantitation Limits by SW 846 and CLP
Anaiyte
SW846
Preparation/
Analysis
SW 846 PQL,
ug/L (1)
CLP CRQL,
ug/L (2)
Pesticides
endrin
lindane
(gamma BHC)
methoxychlor
heptachlor
toxaphene
chlordane (4)
3510or3520/
8080B
3510or3520/
8080B
3510or3520/
8080B
3510 or 3520/
8080B
3510or3520/
8080B
3510or3520/
8080B
0.06
0.04
1.76
0.03
2.4
0.14
0.10
0.05
0.05
0.05
5.0
0.05
Herbicides
2,4-D
2,4,5-TP (Silvex)
8150A
8150A
12
2.0
(3)
(3)
(1) PQL = Practical Quantitation Limit = EQL = Estimated Quantitation Limit
(2) Contract Laboratory Program, Statement of Work for Organic Analysis, OLM01.8
(3) No CLP methods exist for these compounds.
(4) SW-846 quantitation limits are for technical* chlordane. CLP quantitation limits are for alpha and gamma
chlordane.
3-26
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Table 3-6 Quantitation Limits for Volatile TC Constituents
Volatiies
benzene
carbon tetrachloride
chloroform
chlorobenzene
1 ,2-dichloroethane
1 , 1 -dichloroethylene
(1 , 1 -dichloroethene)
methyl ethyl ketone
(2-butanone)
tetrachloroethylene
(tetrachloroethene)
trichloroethylene
(trichloroethene)
vinyl chloride
SW 846 Preparation/
Analysis
8240B or 8020B
8240Bor8010B
8240Bor8010B
8240Bor8010or
8020B
8240Bor8010B
8240Bor8010B
8240B (2) or 8015
8240Bor8010B
8240Bor8010B
8240Bor8010B
SW846
8240 PQU
ug/L (1)
5
5
5
5
5
5
100
5
5
10
CLP
CRQL,
ug/L (3)
10
10
10
10
10
10
10
10
10
10
(1) PQL = Practical Quantitation Limit = EQL = Estimated Quantitation Limit
(2) Poor purging efficiency by this method produces a high detection limit.
(3) Contract Laboratory Program (CLP) Statement of Work for Organic Analysis, OLM01.8
3-27
-------
Table 3-7 Quantitation Limits for Semivolatile TC Constituents
Semivolatiles (BNAs)
o-cresol
(2-methylphenol)
m-cresol
(3-methylphenol)
p-cresol
(4-methylphenol)
1,4-dichlorobenzene
2,4-dinitrotoluene
i
hexachlorobutadiene
(hexachloro-1 ,3-butadiene) (4)
hexachloroethane
hexachlorobenzene
nitrobenzene
pentachlorophenol
pyridine
2,4,5-trichlorophenol
2,4,6-trichlorophenol
SW846
Preparation/
Analysis
3510/8270B
3510/8270B
3510/8270B
3510or3520/
8270B
3510or3520/
8270B
3510 or 3520/
8270B
3510or3520/
8270B
3510or3520/
8270B
3510or3520/
8270B
3510 or 3520/
8270B
3510 or 8270B
3510or3520/
8270B
3510or3520/
8270B
SW 846 PQL,
ug/L (1)
10
10
10
10
10
10
10
10
10
50
ND(2)
10
10
CLP CRQL,
ug/L (5)
10
(3)
10
10
10
10
10
10
10
25
(3)
25
10
(1) PQL = Practical Quantitation Limit = EQL = Estimated Quantitation Limit
(2) ND = Not Determined. If these methods are used, the method detection limits must be determined.
(3) These anatytes are not routinely pan of the CLP method. If required for TC, these analytes must be
specially requested. The CLP 2/88 extraction procedure must be used for the TC semivolatile analytes if
these analytes are desired.
(4) Other methods quantitate this in the volatile fraction.
(5) Contract Laboratory Program, Statement of Work for Organic Analysis, OLM01.8
3-28
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3-29
-------
3-30
-------
o
3-
03
CD
-------
Chapter 4
OVERVIEW OF THE TCLP METHOD
\ * •
Preliminary Sample Preparation
Leaching Procedure for Non-Volatiles
Leaching Procedure for Volatiles
TCLP Method Quality Control
-------
4.0 OVERVIEW OF THE TCLP METHOD
This chapter provides an overview of the TCLP method. Appendix I of this
document includes a copy of the method and Appendix III provides worksheets
which will be useful in understanding method calculations. The following topics
are covered in this chapter:
• Preliminary sample preparation for leaching
• Leaching procedure for non-volatiles
• Leaching procedure for volatiles
• TCLP method QC
4-1
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4.1 Preliminary Sample Preparation for Leaching
Prior to performing the leaching procedure, several preliminary determinations
must be made. These include:
• Are there enough solids present for the leaching process?
• Is particle size reduction required?
• Are immiscible liquids present?
• Which leaching fluid should be used for non-volatile analytes?
Figure 4-1 provides a flow chart which delineates preliminary determinations. The first step is
to take 100g of the waste, pass it through a 0.6 to 0.8 urn filter up to 50 psi and determine
the percent solids. If the percent solids are greater than or equal to 0.5% on a dry weight
basis, the solid must be leached. Any material which remains in the filtration apparatus is
considered a solid. When liquids remain on the filtration apparatus because they are too
viscous to pass through the filter, they are treated as solids. Any material which passes
through the filter is the filtrate and considered a liquid. Therefore, viscous oils which do not
pass through the filter are classified as solids. Oily waste will be discussed further at the end
of this document If the percent solids are less than 0.5%, the filtrate is the TCLP extract, and
the laboratory analyzes the filtrate.
Particle Size
If the percent solids is > 0.5%, the laboratory analyst must determine whether particle size
reduction will be required.
• The requirement is not to measure the size. However, the surface area and particle
size must conform with one of the following criteria:
The solid must have a surface area per gram of material equal to or greater
than 3.1 square centimeters.
The solid must be smaller than 1 cm in its narrowest dimension (i.e., pass
through a 9.5 mm (0.375 inch) standard sieve).
• If the particle size is too large, cutting, grinding, or crushing may be utilized to
decrease particle size.
Choosing the Leaching Solution
Rgure 4-1 shows the determination of the type of leaching fluid for use. If the solid content is
greater than or equal to 0.5%, and if the sample is being analyzed for metals or semivolatiles,
the type of leaching solution must be determined. Note that the leaching solution
determination step requires a smaller (1 mm) particle size than the analytical method because
the leaching solution determination allows much less contact time between the leaching
solution and the sample.
4-2
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After weighing a 5.0 g subsample of the solid; adding 96.5 mL of reagent water, and stirring
for 5 minutes, the pH is measured. lf:the pH is <_5:0, fluid #1 is used. If the pH is > 5.0,
3.5 ml of 1N HGI is added. The mixture is iheated to 50*C for 10 minutes and d>oled. If the
measured pH is less than 5.6, fluid # 1 is used, -if^thefpH;is greater than 5.0, extraction fluid
#2 is used.
The heating cycle is a critical step. After the sample has been heated, it should be cooled to
room temperature. The pH must be measured: immediately after the sample has reached
room temperature. If the solid waste does not remain in contact with the acidic solution
under specified time and temperature conditions, an erroneous pH may be measured.
The leaching fluid for all volatiles is fluid #1. Fluid #1 is an acetic acid and sodium hydroxide
buffer of pH 4.93 ±0.05. Fluid #2 is an acetic, acid solution of pH 2.88 ± 0.05.
4-3
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4.2 Leaching Procedure for Non-Volatiles
The non-volatiles include semivolatile organics, which are also called base,
neutral, and acid extractables (BNAs), pesticides, herbicides, and metals. If the
percent solids exceeds 0.5%, the solid is leached with the appropriate extraction
fluid after any required particle size reduction. The following topics are discussed
in this section:
• Determination of extraction fluid weight
• Sample and OC sample volumes
• Extract, volumes required
• Issues when dealing with multi-phasic waste
• Initial filtrate versus TCLP leachate
The non-volatile extraction or leaching process is outlined in Rgure 4-2. The extraction
process includes placing the sample and appropriate fluid in the bottle extraction vessel and
tumbling for 18 ± 2 hours and filtering the extract for subsequent analysis. The bottle
extraction vessel is described in Section 4.2.2 of Method 1311, which is Appendix I of this
document. In order to generate scientifically valid and legally defensible data, appropriate
weights of environmental samples and leaching fluids must be used.
4-5
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Figure 4-2
Nonvolatile Extraction
^Complete preliminary
[determinations. Figure 4-1.
Sample is 100%
solids.
Weigh out at least
100g of sample.
Multiphase sample. Filter a weighed
amount of sample to produce enough
solids which, when extracted, will
create sufficient extract for all
analyses. (100g minimum.) It may be
necessary to perform % solids on
exact sample used for this extraction
due to subsampling error.
I
Solid
Solids are «0.5% of
sample. Filter
enough sample to
provide for all
analyses. Discard
solids. Filtrate =
TCLP extract
If particle size reduction is needed,
decrease size until waste solids will pass
a 9.5mm sieve (3/8")
Liquid
Phase
Quantitatively transfer solids to an
extraction vessel. Include filter used to
separate phases if sample was
mnltinhagir
Add an appropriate amount of extraction
fluid to the extraction vessel. (Fluid weight
=20 x solids weight)
Close extraction vessel using Teflon tape
and secure in rotary agitation device.
Rotate at 30 ± 2rpm for 18 ±2hrs. Ambient
temperature of extraction room shall be 23
±2eC.
Filter slurry through glass filter fiber (acid
wash if metals are measured). Several
filters may be used. Discard solids. Collect
filtrate.
Analyze liquids
separately and
combine results
mathematically
according to
volume ratio of
original phases.
IS filtrate mtscible
with initial filtered
liquid if sample was
multiphase?
Re
*st
— Yes— fc
stain filtrate.
3reat4'C.
i
r
Combine initial
liquid with
filtrate. This
becomes the
TCLP extract
Immediately after TCLP extract is produced,
record the pH of the extract (For immiscible
liquids, record the pH of each.)Aliquot and
preserve the extract. Unless analyzed
immediately, store aliquot at 4 °C until analyzed.
4-6
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Determination of Extraction Fluid Weight
The following formula is used to compute the required weight of TCLP extraction fluid:
Weight of Extraction = 20 x %Solids x Weight of Waste Rltered
Fluid 100
The amount of extraction fluid required per extraction is 20 times the weight of wet filtered
solids used in the extraction.
A minimum of 100g of waste material must be filtered to generate the solids utilized in the
extraction. If the sample is 100% solids, a minimum of 100g must be used in the extraction.
When aqueous environmental samples contain between one-half and ten percent solids,
several kilograms of sample are required for analysis.
Sample and QC Sample Volumes
The generation of sufficient extract volume to perform all analysis is critical.
• The required volumes vary with the laboratory. Check with the laboratory for actual
volumes.
« Depending on which metal analytes are selected, two or three digestions may be
required.
• If matrix spikes or duplicates are performed, additional volume will be required. Labs
may charge additional fees for these QC samples.
Table 4-1 Volume of Extract Required for One Nonvolatile Analysis
Analysis Type
BNA
Chlorinated Pesticides
Herbicides
Metals
Volume of TCLP Leachate Typically
Required per Test
1 L
1 L
1 L
300 mL/digestion
The previous table outlines the "typical" volumes of extract or total leachate required for non-
volatile analysis. These volumes may vary with the laboratory, tt is imperative that you check
with the lab as to the amount of waste required for their analysis process. The amount of
waste varies with the percent solids. The lower the percent solids, the more waste will be
needed for TCLP preliminary and final testing. If the waste sample is a filterable liquid with
less than 0.5% solids, the volume listed in the previous table can be used as a guide for the
minimum volume needed for the analysis.
4-7
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Issues When Dealing with Multi-phasic Waste
• Subsampling stratified waste is difficult. Therefore, the analyst should consider
calculating percent solids from the same sample container used for the TCLP
extraction instead of compositing all the sample containers. This is the largest source
of error in the TCLP leaching process. The laboratory must consider the amount of
each phase present in each bottle and adjust the calculations accordingly.
• The particle size of multi-phasic material may be difficult to assess. The lab should
identify procedures to classify multi-phasic samples which are not amenable to size
measurement.
• Five grams of sample are usually used to determine the appropriate TCLP leaching
fluid. If there is not enough volume of any individual phase, less material may be
used.
• The pH of the filtrate should be recorded. This provides useful information when
validating field or laboratory duplicates.
• The filtrate volume should also be measured. This information will be needed if the
multiple phases must be mathematically combined.
Initial Filtrate Versus TCLP Leachate
Two liquids are generated when a multi-phasic waste is analyzed.
• Initial filtrate
• Leachate
• If the filtrate is miscibie with the leachate, the two solutions are mixed prior to analysis.
• If the two solutions are not miscibie, they are analyzed separately, and the results
combined mathematically.
The mathematical calculations are performed via the following equation if the TCLP filtrate
and extract are not miscibie.
Final analyte =
-------
After generating the TCLP extract, the pH of the extract should be recorded. If the filtrate and
TCLP extract are mixed, record the pH of the mixture as well as the original TCLP extract
and filtrate. The TCLP extract or filtrate/extract mixture should be aliquoted for each analysis.
Matrix spikes for all subsequent analyses must be added at this time.
The metals aliquot should be preserved to a pH<2 with nitric acid. Adjust the pH of a small
portion of the TCLP extract or mixture prior to adjusting the entire metals aliquot. If a
precipitate forms, do not adjust the pH of the sample extract. If nitric acid is not added, the
sample should be analyzed as soon as possible after TCLP extraction. Metals analysis must
include digestion prior to analysis. Aliquots for BNAs, herbicides and pesticides do not
require chemical preservation. All aliquots must be stored at 4*C ± 2CC prior to analysis.
Example
The following example demonstrates how to calculate the weight of extraction fluid required
to perform a TCLP extraction. In this example, the environmental sample contains 40%
solids. Only metals will be analyzed since the waste is from a metals finishing shop.
In order to determine the total amount of waste required to generate 100g of solids, the
following equation is used:
Amount of multi-phasic material = (10.000)/ (weight percent wet solids)
If 100g of original waste yields 40g of solid, the total amount of waste required to generate
100g of solid is 250g.
250g of total waste required = 10,000/40
Using the equation in Section 7.2.11 of Method 1311 (Appendix I):
Weight of extraction = 20 x % solids x weight of waste material filtered
fluid 100
20 x 40 x 250g = 2,000g of extraction fluid
100
Labs typically assume a density of 1 g/mL for the extraction fluid. Also, note that 40% is
used, not 0.40, for the percent solids. Since 300 mL of extraction fluid is required for one
complete metals digestion, using 250g of the multi-phasic waste will provide enough volume
for the metals analysis. This fallows enough volume to analyze one matrix spike. The use of
matrix spikes will be discussed in the QC section of this chapter. The matrix spike sample
size requirement is the same as for original environmental sample analysis.
4-9
-------
If organic analysis were required, at least three times as much waste would have been used
in the TCLP extraction. For matrix spikes analyses, a triple volume of TCLP leachate will be
required. The terms analytical batch and waste type are not defined in the TCLP regulation.
Most methods, including CLP and SW-846, indicate that a batch is the number of samples
processed through preparation and analysis simultaneously, and should not exceed 20
samples of the same matrix. Most methods require that matrix spikes and matrix spike
duplicates (MS/MSD) for organics be performed at 1 MS/MSD per processed batch, with a
batch containing no more than 20 samples.
4-10
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4.3 Leaching Procedure for Volatiles
Volatile organics are leached using different equipment than non-volatiles.
Rgures 4-3 and 4-4 are the flow charts describing the volatile leaching procedure using the
Zero Headspace Extractor (ZHE). The ZHE must be used when leaching volatiles. In order
to minimize evaporation of volatiles, the volatile leaching procedure is performed on a
separate aliquot of waste. Once the percent solids has been determined in the preliminary
sample preparation phase, a second aliquot of the waste is used to generate the volatile
analysis extract. In all cases, no more than 25g of solids should be placed in the ZHE
because the total volume of the ZHE is 500-600 mLs. In order to prevent the loss of volatile
compounds, heating or excessive sample manipulation must be kept to a minimum. The
samples and equipment used in the process should be cooled to 4°C when possible to
prevent loss of volatiles.
If the sample contains less than 0.5% dry solids, the filtrate is defined as the TCLP extract.
The solid is discarded in this instance. The filtrate is collected in either a Tedlar bag or a
glass syringe which is described in the equipment section of the procedures in Appendix I of
this document. This filtrate becomes the TCLP extract.
Weight of Waste Charged to the ZHE
If the solids are > 0.5% dry solids, the material must be extracted.
If the solids are > 0.5% and < 5.0 %, a 500 g subsample of the waste is weighed
and recorded.
If the solids are > 5.0%, the following formula is used to determine the amount of
waste to place in the ZHE:
Weight of Waste = 25 x 100
Charged in ZHE Percent wet solids
If the solids are greater than 0.5% and the sample is multi-phasic, any solids must be
examined for particle size prior to filtration. The sieve is not used to verify particle size for the
volatile sample. Particles are measured with a ruler and should be less than 1 cm diameter.
Any particle size reduction should be done with minimal exposure to air and without heat
production. All apparatus used in this process should be cooled to 4*C.
4-11
-------
Figure 4-3
Volatile by ZHE
CComplete preliminary
solids determination. Fig.
£1
Solids are <0.5%of
sample. Filter sufficient
sample through ZHE to
provide for all analysis.
Discard solids. Filtrate =
TOP extract
•4-No—| Is the amount of filterable solids^ Q.5%?
Yes
Place the ZHE piston in body of the ZHE
and adjust position of piston to minimize
distance piston will travel when charged
rtth samnle
Store at 4 °C under
minimal headspace and
analyze.
Solids are >5%.
Weigh (2500 / %
solids).
Adjust particle size of solids, if necessary, so size is <1
cm in its narrowest dimension. DO NOT SIEVE,
measure with ruler. Adjust without heat production and
with minimal air exposure.
Quantitatively transfer sample quickly to ZHE. Secure
filter and support screen to top flange and attach top
flange to body of ZHE. Tighten all fittings. Place
vertically with gas inlet/outlet valve down.
Yes-
Does sample contain liquid phase? —No
Attach the gas line, open the
gas inlet/outlet valve and apply
gentle pressure (1-10psi) to
force all headspace form ZHE.
When liquid first appears, close
liquid inlet/outlet valve and
discontinue pressure.
Sample is 100% solids. Attach
gas line to gas intlet/outlet
valve, open liquid inlet/outlet
valve, and gradually apply
pressure in 10 psi increments
until 50 psi is reached.
Liquid Phase
Attach ore-weighed filtrate
collection container to liquid
inlet/outlet valve. Open liquid valve
and gradually apply pressure in 10
psi increments until 50 psi is
reached. After no further liquid is
expelled after 2 minutes at 50 psi,
dose valves, disconnect and
weigh filtrate collection container.
Solid .
-Phase
Add an appropriate weighed
amount of extraction Fluid #1 by
pumping in through the liquid
inlet/outlet valve. (Fluid weight = 20
x solids weight)
Store filtrate at 4 °C under minimal
head space. See Fig. 4-4.
Rotate ZHE end-over-end 2 or 3 times.
With liquid inlet/outlet valve pointed
up, pressurize ZHE to 5-10 psi, and
bleed off any air which might have
been introduced with the extraction
fluid. Close the liquid inlet valve and
pressurize to 5-10 psi ana in
Connect preweighed
filtrate/extract collection
container to liquid i/o valve.
Apply up to 50 psi in 10 psi
increments. See Fig.4-4.
-30 i
Place ZHE in rotary device and
rotate at 30 ± 2rpm for 18 ± 2 hrs in a
room held at 23± 2" C.
unecK pressure in £i-it oy
quickly opening and closing
the gas inlet valve. Is
pressure present?
-No*
ZHE leaked.
Re-extract
sample.
4-12
-------
Figure 4-4
Volatiles by ZHE Continued
Store initial filtrate at 4 °C under
minimal head space. See Fig. 4-3.
Analyze liquids
separately and
combine results
mathematically
according to
volume ratio of
original phases.
Connect preweighed
filtrate/extract collection
container to liquid input/
output valve. Apply up to 50
psi in 10 psi increments.
Collect the extraction filtrate.
See Fig.4-3.
-No —
Is filtrate miscible
with initial filtered
liquid if sample was
multiphase?
-Yes-
Combine initial
liquid with
filtrate. This
becomes the
TCLP extract
Store at 4 °C under minimal head space
prior to analysis.
4-13
-------
All waste which remains in the ZHE after reaching a pressure of 50 pounds per square inch
(psi) is considered solid phase and undergoes leaching. Any liquid which is removed during
filtration is considered liquid phase filtrate. The filtrate is captured in either a Tedlar bag or
glass syringe. The solids are leached with fluid #1.
If the percent solids is 100%, a 25g sample of the solid is placed in the ZHE after any
necessary particle size reduction is performed. The particle size reduction follows the same
protocol requirements as volatile extraction of waste with solids content greater than 0.5% but
less than 100%. The extraction is similar to the TCLP extraction of multi-phasic material.
When performing TCLP extraction for volatile analysis, extraction fluid #1 is always used.
The quantity of extraction fluid is 20 times the solid waste weight used in the extraction.
The extraction is performed by placing the ZHE in the rotary agitator at 30 ± 2 rpm for
18 +2 hours. The ambient temperature is maintained at 23 ±2°C during agitation. At the
end of the agitation period, the ZHE piston pressure must be measured to verify that
pressure was maintained during the extraction. If pressure was not maintained, the extraction
must be repeated after the ZHE is examined for mechanical problems. If the pressure was
maintained, the material in the ZHE is separated into solid and liquid phases by pressure
filtration. A small amount of the liquid extract should be examined for miscibility with the
previously captured filtrate. If these fluids are miscible, the liquid extract and the filtrate may
be stored in the same container (Tedlar bag or syringe) with minimal or no headspace. This
mixture becomes the TCLP extract for volatile analysis. If the two fluids are not miscible, they
are stored in separate containers with minimal or no headspace. The volatile analysis are
performed separately and combined mathematically using the same equation as for the non-
volatile analysis. All extracts and fluids are kept at 4eC _+2°C prior to analysis.
4-14
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4.4 TCLP Method Quality Control
• TCLP extraction blank
• Method preparation blanks
• Calibration
• Matrix spikes
BIAS CORRECTION IS NO LONGER REQUIRED.
• Method of standard additions
TCLP Extraction Blanks '
• A minimum of one TCLP extraction blank is generated for every 20 extractions
processed in a given extraction vessel using the same fluid. Most labs have multiple
extraction vessels. The common industry strategy is to generate one TCLP extraction
blank for each group of samples processed simultaneously using the same batch of
fluid.
Calibration
• Calibration should follow the respective method requirements. Typically a three to five
point initial calibration followed by a single point continuing calibration is specified.
Method Preparation Blanks
• Preparation blanks performed for a specific analysis should follow the frequency and
requirements of the method. Typical requirements are one per preparative batch from
similar matrix for every 20 samples.
Matrix Spikes
• Matrix spikes are used to monitor the performance of the analytical methods on the
matrix and to assess the presence of interferences.
• A matrix spike shall be performed for each waste type (waste water, soil, etc.) unless
the result exceeds the regulatory level and the data are being used solely to indicate
that the regulatory level is exceeded.
• A minimum of one sample from each 'analytical batch' must be spiked. For spike
samples, a double or triple volume of TCLP leachate will be required. The term
analytical batch is not defined in the regulation. Most methods, such as CLP and
SW846, indicate that a batch is no more than 20 samples of the same matrix
4-15
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processed through preparation and analysis simultaneously. Based on this criteria,
the minimal matrix spike frequency of analysis is one per 20 samples. However,
many process batches may include from one to 19 samples and the frequency may
increase with fewer samples processed. Some EPA Regions define each type of
waste as a matrix, and: require matrix spikes for each matrix.
• Matrix spikes (MS) are to be added after leaching and filtration but prior to
preservation. Spikes are NOT to be added prior to the TCLP leaching.
• The spike should be added to the same nominal volume of TCLP extract as the
unspiked sample.
• The spike concentration "should" be added at the regulatory level. If the expected
concentration in the sample is as low as half the regulatory level, the spike
concentration can be decreased to half the regulatory level. In all cases, the spike
must be greater than 5 times the method detection limits.
• Matrix Spike Recoveries are calculated by:
%Recovery = 100 ( Measured value for the spiked sample minus measured
value of the unspiked sample)/ known value of the spike
• When the matrix spike recovery falls below the expected analytical performance,
alternate methods of analysis may be required to measure analyte concentration in
the TCLP extract. The matrix spike recovery limits from the Contract Laboratory
Protocol methods are used when the method is used.
If the matrix spike recoveries exceed limits, other analytical methods such as isotopic
dilution may be used to deal with the matrix effects. Typically, the holding times will
be exceeded or near the limits when this occurs. If possible, resampling of the waste
may be required to assure that the appropriate method is used and holding times are
met.
• B/as correction is no longer required.
Surrogate Spikes
Surrogates are compounds which are not expected to be in the samples but are chemically
similar to those being determined. The concentrations and specific compounds are listed in
the appropriate methods. The recovery of the compounds are monitored with specific criteria
either being found in the method or determined by statistical quality control in the laboratory.
Method of Standard Addition
Four equal volume pre-digestion aliquots of sample are measured and known amounts of
standards are added to three aliquots. The fourth aliquot is the unknown and no standard is
added to it The concentration of standard added to the first aliquot should be 50% of the
expected concentration. The concentration of standard added to the second aliquot should
be 100% of the expected concentration and the concentration of standard added to the third
4-16
-------
should be 100% of the expected concentration and the concentration of standard added to
the third aliquot should be 150% of the expected concentration. The volume of the
unspiked and spiked standard should be the same.
In order to determine the concentration of analyte in the sample, the analytical value of
each solution is determined and a plot or linear regression performed. On the vertical axis
the analytical value is plotted versus the concentrations of the standards on the horizontal
axis. An example plot is shown in Figure 4-5. When the resulting line is extrapolated back
to zero absorbance, the point of interception of the horizontal axis is the concentration of
the unknown.
o
c
e
Zero
Absorbcnee
Concentration
l Cone, of
Sample
Aden 0
No Addn
Addn I
Addn of 50%
of Expected
Amount
Addn 2
Addn of 100%
of Expected
Amount
Addn 3
Addn of 150%
of Expected
Amount
F16URE4-5 STANDARD ADDITION PLOT
4-17
-------
When must Standard Addition be used?
The method of standard additions is used for metallic contaminant determinations if both of
the following criteria are met:
1. The matrix spike recovery from the TCLP extract is less than 50% and the unspiked
sample concentration is less than the regulatory level.
2. The contaminant measured in the sample is within 20% of the regulatory level.
For the method of standard additions to be correctly applied, the following limitations must
be taken into consideration:
« The plot of sample and standards must be linear over the concentration range of
concern. For best results, the slope of the line should be similar to that of a plot of
the aqueous standard.
o The effect of the interference should not vary as the ratio of the standard added to the
sample matrix changes.
Holding Times
As previously discussed in Section 3, the holding times must be met. Sample data which
exceed holding times are not acceptable for verifying that a waste does not exceed
regulatory levels. However, if TCLP extract concentrations exceed regulatory action levels,
and holding times are exceeded, the data are considered minimum values, and the data are
considered valid.
4-18
-------
o
Q>
CJl
-------
Chapter 5
DATA VALIDATION AND
DATA DELIVERABLES
-------
5.0 DATA VALIDATION AND DEUVERABLES
This chapter addresses the following questions:
• What is data validation?
• When must TCLP data be validated in EPA Region 2?
• Which analytical deliverables are needed to validate TCLP data when
utilizing the USEPA Region 2 Organic, Inorganic, and TCLP Data
Validation Protocols?
• Which analytical deliverables are recommended for TCLP data which will
not be validated?
• How should these deliverables be utilized to assess data quality and
usability?
5-1
-------
5.1 Data Validation
What is Data Validation?
"Data validation is a systematic process for reviewing a body of
data against a set of criteria to provide assurance that the data are
adequate for their intended use. Data validation consists of data
editing, screening, checking, auditing, verifying, certifying and
reviewing.11 (EPA Region 2 CERCLA QA Manual)
The most important criteria which the data reviewer evaluates are:
1. Holding times
2. Instrument tuning
3. Calibration and retention time windows
4. Blank contaminants
5. Surrogates (a measure of extraction efficiency)
6. Chromatographic performance (baseline, interference, retention time shift and peak
resolution)
7. Emission interferences or spectral interference from other elements when reviewing
metals data
8. Calculations
9. Transcription of numerical values to the required forms in the data package
10. Matrix effect errors; interference from the sample itself
11. Degradation of compounds during analysis
There is a substantial amount of uncertainty in all chemical data. In addition to lab error,
there are field sampling errors, such as improper decontamination of field equipment, air
bubbles in VOA vials, loss of samples, and failure to ship samples in a timely manner after
collection. Different analytes have varying degrees of uncertainty.
TCLP data are expected to have significantly more inherent error than routine chemical
analysis because additional procedures are performed by the laboratory analyst.
5-2
-------
What is data qualification?
Qualifying data is a method of notifying the data user that some data have additional
uncertainty. The Region 2 TCLP data validation protocol qualifies analytical data with the
following flags:
• R Rejected (unusable)
• J Estimated
• UJ Estimated detection limit
• N Presumptively present (cannot positively identify an analyte)
• JN Presumptively present at an estimated concentration
The above qualification "flags' provide QC information to the data user. The Region 2 TCLP
data validation protocol qualifies analytical data as unusable, estimated, presumptively
present, or presumptively present at an estimated concentration.
Unusable data are rejected and qualified with an "FT. When data are rejected, it doesn't
mean that the analyte wasn't there - it means that either the test was not correctly performed
or that the test was not appropriate for the matrix. Examples of reasons for rejecting data
include: poor calibration, low surrogate recoveries, and air bubbles in volatile sample vials. If
the data are needed, resampling and reanalysis must be performed. For example, the
holding time for TCLP VOAs is 14 days from sampling until TCLP leaching, and then 14 days
until analysis. If a sample is held for 30 days from collection until leaching, all non-detects
and positive results below regulatory action levels will be rejected because analytes could
have been present above regulatory action levels. Results above the regulatory action levels
would be accepted. However, the site owner may still want resampling and reanalysis to
assure that a false positive did not occur.
When data are qualified as estimated with a "J", it means that the data should be used with
caution. The data are significantly imprecise, and the reported value given is little more than
an estimate. Estimated means that the compound is present, but the exact concentration is
uncertain.
When data are qualified with a "UJ", it means that the detection levels are uncertain. For
example, this qualifier would be used when surrogate recoveries in organics are greater than
10% but not within the method criteria. The "UJ" notifies the data user that the detection limits
are estimated.
When the analyte identity is uncertain, the qualifier °N° is used to indicate that it is
presumptively present. This is used in data validation when a mass spectrum differs slightly
from the required spectral criteria. Data validators use the qualifier °JN°, presumptively
present at an estimated concentration, much more often than the qualifier "N". The'JN" flag
denotes both qualitative and quantitative uncertainty. This is typically used when tentatively
identified compounds (TICs) from semivolatile gas chromatography/mass spectrometry
analysis are presented. The concentration and identities of the TICs are uncertain and are
flagged with °JN°.
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When Must TCLP Data Be Validated?
EPA Region 2 requires TCLP data for RCRA RFIs and many types of CERCLA sampling
events to be validated. The RCRA program does not explicitly require the validation of
routine TCLP analysis of waste materials to determine compliance with TC or LDR
regulations.
Data validation reduces false negatives, false positives, and misquantitation in reported data.
Misquantitation includes both laboratory arithmetic errors, and data qualified as estimated or
presumptively present because of analytical problems. The costs for TCLP validation are
quite variable, and depend specifically on which tasks the data user instructs the data
validator to perform, and the quality of the laboratory analyzing the environmental samples.
The cost of validating a single sample containing the 39 TC analytes is about $300-3500 per
sample analyzed by a competent laboratory. In addition to the data validation cost, the
laboratory will charge an additional fee, estimated at $200-$400 per sample, for generating
analytical deliverables. The more a data user knows about a specific waste, the less useful
data validation becomes. For example, if the data user knows which raw materials, final
products, and by-products are in a waste, and has historical data that demonstrates that the
TC analytes in the TCLP extract are far below regulatory action levels, TCLP validation would
not be cost effective. Alternatively, when the data user has very limited knowledge of a
waste's characteristics, decisions based on that data can result in significant disposal cost for
management. Therefore, many businesses believe that it is prudent and cost effective to
validate this type of TCLP data.
Some regulatory agencies, especially in the CERCLA program, do not allow laboratories to
validate their own data. All laboratories review their own data for contractual compliance and
analytical problems. Unfortunately, this assessment of contractual compliance may also be
called data validation. Many laboratories now call their contractual compliance review "data
review' to differentiate this review from data validation.
Contractual compliance is NOT the same as data validation. A lab can contractually fail and
still produce technically valid data. An example of this occurrence is when contractual
requirements for metals data indicated that results would be delivered to the client 40 days
from receipt of the sample. If the laboratory did not deliver for 60 days, the laboratory failed
the contract criteria, but the technical criteria were still met. Alternatively, a laboratory can
contractually meet criteria but: produce data which is not useable.
In order to validate TCLP data, the following must be ascertained:
• Are any specific data validation protocols required by a regulatory agency?
• What are the regulatory action levels?
The TC regulatory action levels are listed in Table 1. The Land Disposal Restrictions
regulatory action levels are listed in Appendix II.
The EPA Region 2 TCLP, Inorganic and Organic Validation protocols are included in
Appendix IV. If your region or state does not have a TCLP validation procedure, the Region
2 data validation protocol may be used. If the applicable sampling and analysis plan requires
5-4
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regulatory approval, the data user, lab and regulator must agree on validation criteria prior to
sample collection.
Phenols
When validating TCLP phenols, the TCLP extraction fluid may cause a matrix effect. This
matrix effect may lower surrogate and matrix spike recoveries for phenols. As long as the
matrix spike and surrogate recoveries are above 10%, the data should not be rejected. If a
matrix effect precludes acceptable pyridene or phenols surrogate and matrix spike recoveries,
a facility should request a meeting with the appropriate regulatory agency to discuss alternate
methods for determining whether a solid-waste exhibits TC. . .
After determining whether the project will require validation, the.appropriate deliverables must
be specified to allow the; validation to occur. For example, if the validation requires
calibration verification, raw instrument calibration data must be present for the validation to be
performed.
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5.2 Data Deliverables
General TCLP Data Deliverables
In order to validate and assess TCLP data, appropriate deliverables must be
specified. Deliverables will differ depending on whether validation is required.
These analytical deliverables must be specified before samples are collected.
The following topics are discussed:
• Deliverables when no validation is required
• Additional deliverables which may assist in review
• USEPA Region 2 analytical deliverables
• Specifying data deliverables
Deliverables When No Validation is Required
When TCLP data are not validated, we recommend that the laboratory furnish the data user
the following deliverables:
1. Sample description and sample identification numbers.
2. Analytes, concentrations, and units.
3. Level of contaminant(s) in method and TCLP blanks.
4. Matrix spike, QC check sample when applicable, and surrogate recoveries.
5. A description of matrix problems and analytical problems observed during analysis,
and an assessment of how those problems will affect data usability.
6. A certification that samples were analyzed within method holding times (from the date
of sample collection). This certification must include the sampling date, TCLP
extraction dates, preparatory extraction dates, and analysis dates.
The laboratory staff are not always familiar with data validation protocols or with data usability
on a project specific level. Therefore, in addition to information about the QC supplied by the
laboratory, it may be beneficial to work with a specialist in this area. Some firms specialize in
validating and assessing data quality.
5-6
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Additional Deiiverabies Which May Assist in Review
While the data is the key factor, some information is not always captured in the analytical
result. For example, if a procedure is modified due to a matrix problem, the procedure must
be documented and the validator provided this information. The following information may
facilitate validation.
• Chain of Custody records
• Analytical procedures used by the laboratory
• An example of a data calculation
The data user must specify the information (analytical deliverables) desired from the
laboratory. If this is not done, only the final result, or the final result plus a QC summary, will
be provided.
Region 2 Analytical Deliverables
The following TCLP analytical deliverables are required by the Region 2 TCLP data validation
protocol:
1. The TCLP and preparative extraction dates and analysis dates.
2. Selection of extraction fluid data.
3. A physical description of the samples.
4. The sample weights and the extraction fluids weights.
5. The final volume of TCLP extract and the volume of extract analyzed.
6. The data used to compute percent dry solids and the weight of the liquid phase (if
applicable).
7. Extraction logs for each sample, indicating the volume and pH of acid added. Were
inorganic sample extracts properly preserved?
8. A description of the materials of construction for extraction vessels, filtration devices,
and ZHE extraction devices (i.e. glass, Teflon, PVC, stainless steel, etc.).
9. The data used to compute TCLP extract concentrations for multi-phasic samples.
10. When VOA samples consist of oily waste that cannot be filtered, describe how the
TCLP aqueous extract is separate from the oily waste.
11. A copy of the sampling log or trip report.*
12. Any evidence of leakage in the ZHE device.
*ltem 11, which requires the presentation of the sampling log, may not be available from the
laboratory. The sampling team may supply this information.
In order to facilitate analysis and validation, Associated Design and Manufacturing
Corporation and Dr. Larry Jackson have developed work sheets (Appendix III) which may be
used by the analytical laboratory to generate the above listed analytical deliverables.
Additional descriptions of requirements and deliverables for modification of CLP analysis of
leachate is presented in Appendix VIII.
5-7
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Specifying Data Deliverable^
EPA Region 2 requires TCLP data to be validated for RCRA RFIs and many types of CERCLA
sampling events.
Specific regulations, as noted in Appendix IX, require SW-846. Many state environmental
agencies require the use of SW-846 methods for hazardous waste determinations.
SW-846 methods cannot be validated by CLP validation criteria because SW-846 methods do
not specify analytical deliverables, and have different QC criteria than CLP methods.
Therefore, validation protocols must be prepared for non-CLP methods such as those in SW-
846. i
For non-CLP methods, data validation criteria must include:
Holding times for sample preparation and analysis
Preparation logs
Calibration
Method and instrument blank data review
Calculations
Matrix spike data
Duplicate results
For organic analysis, the following additional items must be included:
• Instrument tuning if GC/MS is used
• Surrogate recoveries
• Chromatographic performance (baseline, interference, shift and peak resolution)
• Mass spectral interpretation or compound identification
For metals analysis, the following additional items must be included:
• Whether method of standard addition or serial dilution were needed and performed
correctly. The November 24,1992 modification to the TCLP procedure mandates the
use of method of standard additions under certain circumstances.
• Post digestion spike recoveries versus pre-digestion spike recoveries.
• The frequency of analysis of QC samples must be validated.
5-8
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o
1
a>
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Chapter 6
ANALYZING AND ASSESSING MULTI-PHASIC AND
OILY WASTES
Definition of Oily Waste
Problems/Issues
Suggestions
Most Commonly Asked TCLP Question
Analytical Options
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6.0 ANALYZING AND ASSESSING MULTI-PHASIC AND OILY WASTES
Analyzing and Assessing Multi-Phasic and Oily Wastes
This chapter provides strategies which may be beneficial in characterizing oily
wastes. There is no single correct method to analyze these wastes.
• Definition of oily waste
• Problems/Issues
• Suggestions
• Most commonly asked TCLP question
• Analytical options
This chapter outlines the current issues and difficulties in performing TCLP on multiple phase
and oily waste. This chapter is not meant to provide unequivocal answers, but to provide
suggestions and strategies which may be successful. There is no single correct method in
dealing with these materials. The initial discussion in this chapter provides references and
information indicating that EPA understands the difficulties in applying the TCLP to multi-
phasic and oily wastes. Subsequent discussions summarize possible strategies which may
be used in leaching and analysis.
6-1
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6.1 Definition of Oily Waste
Appendix VI contains several papers presented at the EPA's 1992 Waste Testing
& Quality Assurance Symposium Work Shop on oily waste. The following is
Clifford Marquis's of BP Research, definition of oily waste (see Appendix VII):
Although it is nearly impossible to precisely define the term "oily waste",
the following analysis can provide a basis for further discussion:
a) An oil is generally an immiscible or relatively insoluble
liquid, varying in composition but consisting of organic
constituents. Petroleum oil principally consist of hydrocarbons;
.vegetable and animal oils are glycerides, and fatty acids; and
essential oils are terpenes, alkaloids, etc.
b) An oily waste is an industrial process waste or residual
bearing oil in a visual and/or measurable proportions.
c) Oil in oily wastes can occur in any matrix, including:
sorbed to dry solids; in sludges or slurries; multi-phasic liquids or
sludges/slurries with multi-phasic liquids, if water is present
Proper treatment and disposal of all such matrices is a concern of
the petroleum industry.
d) Oily wastes possess a wide variety of compositions and
physical and toxicological properties.
6-2
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6.2 Problems/Issues
Problems with the TC Model
« The model does not differentiate between oily and aqueous liquids.
« The model assumes a person drinks 2 liters a day of well water for 70
years. This assumption is not applicable for oily wastes.
o The disposal scenario depicted by EPA is not an accurate description of
today's practices. For example, liquids are no longer accepted in
municipal landfills.
o The model does not correct for absorption of oily waste on soils. Oil may
also adhere to other landfill matrices instead of mixing with the aqueous
phases.
The difficulty in analyzing oily wastes by TCLP may be categorized as modeling, analytical
and regulatory problems.
The teachability Subcommittee of the EPA Science Advisory Board's Environmental
Engineering Committee has published its recommendations. A copy of this report is in
Appendix VII of this document. This document outlines the properties of an optimum leach
test.
Issues with Oily and Multi-phasic Waste and TCLP
• It is difficult to separate the phases.
• Volatiles may evaporate during handling.
• The tumbling action of the two liter extraction vessel can form emulsions which are
difficult to separate.
• The oily .material may obstruct the filter. When this happens with the ZHE, the test
must be repeated.
• Oily materials often yield oil and aqueous leachate which must be analyzed
separately. This increases costs and time of analysis.
• The method requires determination of dry weight percent solids. When the "solid" is
actually oil or organic, drying can be hazardous and inappropriate. It may be
impossible to achieve a constant weight when performing a percent solids
determination.
6-3
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• When multiple phases and multiple bottles are used in sampling, each container will
show different amounts of each phase.
• It may be impossible to separate solids from oil. If volatiles are analyzed, additional
sample manipulation to remove solids will result in loss of volatiles.
6-4
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6.3 Suggestions
Suggestions for performing TCLP extractions on oily wastes include the
following:
Planning
Regulatory approval
Separate phases for analysis
Documentation of phase type and volumes
As previously indicated, these are suggestions. There are no consistently and absolutely
appropriate methods when performing TCLP extractions on oily wastes.
• Planning is more critical when oily or multi-phasic samples are collected and analyzed.
Discuss the sample matrix with the laboratory before collecting samples.
o Once an approach is formulated, regulatory approval may be needed. This approval
is of greater importance if deviations from the TCLP extraction method are required
due to the matrix.
<> If two liquid phases are present, each phase should be separated and analyzed
individually.
• The SW-846 Methods specify several procedures for analyzing oily waste. BNA
methods include 3580B for preparation followed by 8270B. The pesticides method
includes 3580B using hexane as the extraction solvent followed by 8080B. The VOAs
are analyzed by 8240B. Metals can be prepared by method 3040B and analyzed by
appropriate analytical methods.
• The number, appearance, and volume of each phase should be documented before
collection of the sample. The phase volume can be estimated by measuring the
height of the phase in the container and the diameter of the container. This
information can be used to estimate the amounts of material available for testing.
• Phase volume should be estimated after sample collection and prior to analysis.
• In mufti-phasic liquid samples, the relative density of each phase should be
documented.
6-5
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When multiple containers of multi-phasic waste are received, each container will have
different amounts of each phase. If multiple sample containers are collected and each
container is multi-phasic, the number, appearance, volume and relative density should
be documented for each container.
If regional and state regulators will allow, one container can be mixed and analyzed.
By knowing the volumes in the other sample containers, the total composition can be
mathematically calculated.
If one phase is organic and contains < 0.5% solids, this may be directly characterized
by the appropriate analytical method after filtration without TCLP extraction.
Subsampling increases the possibility of sampling error.
The percent solids should be determined in multi-phasic samples before filling the
ZHE. This prevents overfilling the ZHE.
The TCLP method requires drying the solids at 100CC ± 20CC to determine percent
dry solids. This may not be achievable for organic multi-phasic material because of
safety considerations.' If this cannot be done, the reason should be documented.
The percent wet solids is used to calculate the weight of extraction fluid. If this
occurs, the lab should discuss this with the client prior to using the percent wet solids
as the solids content. This will greatly effect the final analyte concentrations.
Particle size reduction is difficult on oily material because the solids congeal. This is
especially true if the material cannot be dried.
Extreme caution should be taken when adding acid to organic waste. Heating the
organic waste in the presence of acid to 50°C should be done with great caution.
This may be required in order to determine which extraction fluid is used.
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6.4 Most Commonly Asked TCLP Question
I have an oily waste, which flows through a filter. My detection limits are
higher than the regulatory action levels. What should I do?
You have four options:
1. Recycle or burn.
2. Classify by prior knowledge as non-hazardous.
3. Treat the waste as hazardous.
4. If the oil passes through the filter, analyze the TCLP leachate.
1. If the oily waste can be classified as used oil, it can be burned or recycled and a
TCLP analysis is not needed (40 CFR 266.40; 261.6(a)).
2. The waste can be treated as hazardous if no information is available to allow
classification by prior knowledge.
3. By knowledge of the generation of the oily waste, the generator may be able to
certify that the waste could not contain any of the TC analytes at concentrations
above the regulatory action levels. {40 CFR 262.11c(2)). The waste may be a
regulated hazardous waste under other EPA waste code classifications.
4. The liquid which passes through the filter can be analyzed to determine whether it
contains TC analytes. If the SW 846 methods are not appropriate for TC analytes,
any method which is sensitive enough to meet regulatory limits and has
documented QC may be used.
The following pages includes correspondence on oily waste explaining EPA's strategy for
classifying oily wastes as hazardous or non-hazardous.
6-7
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OhbEF*
State of Ohio Environmental Protection Agency
P.O. Box 1049,1800 WaterMark Dr.
Columbus, Ohio 43256-0149 Richard F. Celeste
(614)644-3020 Fax (614) 644-2329 Governor
Ocrober 30, 1990
Gail Hansen
U.S. Environmental Protection Agency
Office of Solid Waste
Methods Section
Washington, D.C. 20460
Dear Ms. Hansen:
I receive many inquiries on SW-846 detection limits. One caller stated that
he had samples analyzed under SW-846 protocol which totaled over $75,000, only
to find that many of the constituents had detections limits above regulated
values. Another caller had industrial waste (baghouse residue) tested under
TCLP and noted that the detection limits of the constituents were all below
regulated levels except for chlordane which in eight out of nine samples was
0.045 mg/L, versus the regulated value of 0.03 mg/L. I need suggestions on
the appropriate response to these inquiries, specifically:
(1) Assuming a given laboratory has followed proper protocol, If
detection limits of constituents in a waste sample are in excess of
but close to regulated values, is the sample considered hazardous?
(2) Using the chlordane situation (above) as an example, what
analytical procedures can a laboratory use, for example clean-up
and dilution, outside of procedures specified under a given method
(eg. TCLP), which are permissible by the U.S. EPA? Can Method 8250
(semi-volatiles) , for example, be used to confirm or as a
substitute for TCLP in analyzing chlordane?
(3) Is there an upcoming FR updating and clarifying analytical problems
in the TCLP analytical section?
Your help will be appreciated in resolving the concerns outlined in this
communication. If you need additional information, I may be contacted at
(614) 644-2956.
Sincerely,
, n^
Art Coleman
Technical Assistance Section
Division of Solid and Hazardous Waste Management
ALC/pas
cc: Karl Bremer, USEPA, Region V Steve McBride, DERR
Dr. Gary Davidson, Chief, Public Health Laboratories, ODH
David E. Vanderberg, Regional Manager, Kemron Environmental Services
Gerry 6. loannides, Chief, EnVfPo-nmental Services, Ohio EPA
6-8
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-fi'-
UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
- WASHINGTON, D.C. 20460
NOV 8 1390 o-«.c£o?
SCU2 WASTE AND EV==G = .NCv RESPCNSr
Art Coleman
Technical Assistance Section
Division of Solid and Hazardous Waste Management
Ohio EPA
P.O. Bex 1049
1800 WaterMark Dr.
Columbus, OH 43266-0149
Dear Mr. Coleman:
I am writing in reponse to your letter of October 30,1990
concerning the questions you raised with Method 1311 (TCLP) .
In answer to your first question, there are situations when
a laboratory is.asked to.perform an inappropriate test. "The TCLP
was not intended to be applied to certain matrices, such as oils
or neat solvents. In these instances, the waste usually goes
through the filter and is, by definition, a liquid and its own
extract. The analysis of this liquid extract for organics
entails diluting it before injecting it into a GC or GC/MS. The
dilution often results in detection limits being much higher than
the regulatory thresholds. If this is the case, you must assume
your waste is hazardous since the laboratory cannot demonstrate
non-hazardousness with TCLP for these materials. We currently do
not have the technology to address this issue.
In answer to your second question, a laboratory must use the
TCLF if testing for hazardousness under the Toxicity
Characteristic or if assessing effectiveness of waste treatment
under the Land Disposal Restrictions Program. These two
regulations actually contain the method as an appendix and it is,
therefore, part of the law. However, the extract obtained from
the TCLP may be analyzed by any method as long as that method has
documented QC and the method is sensitive enough to meet the
regulatory limit. In other words, the lab does not have to use
SW-846 methods because these methods are intended to serve only
as a guidance for the regulated community. SW-846 methods that
are currently in draft form (e.g., 8250 for chlordane) may also
be used to analyze the extract.
6-9 Printed on Recycled Pepcr
-------
In 'answer to your third- question, .there are no plans to
prepare a -clarifying, FR update in the near future.
I hope these answers have sufficiently addressed your
concerns. If you have any further questions, please give me a
call at (202) 475-6722 or write me again at the above address.
Sincerely yours,
Gail Kansen
Health Scientist
Methods Section
(OS-331)
cc: Alec McBride
Jeanne HanJcins
Hugh Davis, OWPE
Leon*Laizarus," 'Region II
6-10
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UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
WASHINGTON. O.C. 20460
SOUD
P *' I *S l">'*'
RECEIVED
Ms. Elaine McPherson |nM « n .QQ.
Technical Sales Representative JUW t u 1331
IT Corporation
17605 Fabrica-Way
cerritos, CA 90701 Toxic & Hap Waste
Dear Ms. McPherson:
I am writing in reference to your letter of April 11, 1991
concerning the handling of TCLP extractions as they apply to oily
wastes.
. ..We. do not recommend performing the extract on the oily waste
that passes through the filter as Margo Jackisch of SAIC
suggested to you. First of all, the TCLP determines release
potential in two steps, the first of which I will discuss here as
it specifically applies to your situation. The initial
filtration step separates the solid phase of a waste from its
liquid phase. This liquid phase represents the primary waste
leachate or the liquid fraction of a waste that is mobile and can
be released from a landfill. In your case, the oil goes through
the filter and, by definition, becomes its own leachate which is
then analyzed directly.
If your waste is a used oil that is destined for recycling,
there is no need to characterize the waste since it would be
exempt under 40 CFR Section 261.6(a) (2) (iii) and (a) (3) (iii) . It
is the decision to dispose of the waste, in lieu of recycling,
that triggers the waste characterization requirement. If your
waste is a used oil that cannot be recycled and is destined for
disposal, generators are required to make a hazard determination.
If the generator chooses to test for the Toxicity Characteristic,
the generator must use the TCLP or an approved alternative
method, as described in 40 CFR 261.24. The extract obtained from
the TCLP may be analyzed by any method, provided the method used
has documented QG and is sensitive enough to meet the regulatory
threshold for the constituents of concern.
In cases where the TCLP results on used oil or oily wastes
are inconclusive, including cases where the detection limit for a
constituent is higher than the regulatory threshold, generators
may use their knowledge of the processes involved in the
6-11
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generation of the waste to make a hazard determination or resort
to an alternative analytical method to get an answer. This has
been necessary with volatile organics; At this time, the Agency
is conducting studies of an automated headspace analysis
methodology coupled with isotope dilution mass spectrometry in
order to achieve greater analytical sensitivity for all TC
volatile analytes, including vinyl chloride. We suggest the use
of this approach where needed. Currently, only a working draft
method (copy enclosed) is available. Pending the outcome of
Agency studies, the draft method will be revised and proposed for
inclusion in SW-846.
For further assistance, please call the MICE (Methods
Information Communications Exchange) at (703) 821-4789. Calls
are recorded on an answering machine and, for the majority of
questions, responses are provided within 24 hours. I hope this
information has sufficiently addressed your questions.
Sincerely yours,
Gail Hansen
Environmental Health Scientist
Methods Section (OS-331)
cc: David Bussard
Alec McBride
Steve Cochran
Mike Petruska
John Austin
Leon Lazarus, Region II
Hugh Davis, OWPE
RCRA/Superfund Hotline
MICE Line
6-12
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* UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
* WASHINGTON, D.C. 20460
•rrrre -r
SOUS '.VAST; i.\; i:Y;ss=\C' =>?£ =
RECEIVED
Ms. Elaine McPherson mj. « „ „.
Technical Sales Representative JUN t u Ib31
IT Corporation
17605 Fabrica Way
cerritos, CA 90701 Toxic & Hap Waste
Dear Ms. McPherson:
I am writing in reference to your letter of April 11, 1991
concerning the handling of TCLP extractions as they apply to oily
wastes .
We ..do not .recommend performing the extract on the oily waste
that passes through the filter as Margo Jackisch of SAIC
suggested to you. First of all, the TCLP determines release
potential in two steps, the first of which I will discuss here as
it specifically applies to your situation. The initial
filtration step separates the solid phase of a waste from its
liquid phase. This liquid phase represents the primary waste
leachate or the liquid fraction of a- waste that is mobile and can
be released from a landfill. In your case, the oil goes through
the filter and, by definition, becomes its own leachate which is
then analyzed directly.
If your waste is a used oil that is destined for recycling,
there is nc need tc characterize the waste since it would be
exempt under 40 CFR Section 261. 6(a) (2) (iii) and (a) (3) (iii) . It
is the decision to dispose of the waste, in lieu of recycling,
that triggers the waste characterization requirement. If your
waste is a used oil that cannot be recycled and is destined for
disposal, generators are required to make a hazard determination.
If the generator chooses to test for the Toxicity Characteristic,
the generator must use the TCLP or an approved alternative
method, as described in 40 CFR 261.24. The extract obtained from
the TCLP may be analyzed by any method, provided the method used
has documented QC and is sensitive enough to meet the regulatory
threshold for the constituents of concern.
In cases where the TCLP results on used oil or oily wastes
are inconclusive, including cases where the detection limit for a
constituent is higher than the regulatory threshold, generators
may use their knowledge of the processes involved in the
6-13
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generation of the waste to make a hazard determination or resort
to an alternative analytical method to get an answer. This has
been necessary with volatile organics. At this time, the Agency
is conducting studies of an automated headspace analysis
methodology coupled with isotope dilution mass spectrometry . in
order to achieve greater analytical sensitivity for all TC
volatile analytes, including vinyl chloride. We suggest the use
of this approach where needed. Currently, only a working draft
method (copy enclosed) is available. Pending the outcome of
Agency studies, the draft method will be revised and proposed for
inclusion in SW-846.
For further assistance, please call the MICE (Methods
Information Communications Exchange) at (703) 821-4789. Calls
are recorded on an answering machine and, for the majority of
questions, responses are provided within 24 hours. I hope this
information has sufficiently addressed your questions.
Sincerely yours,
Gail Hansen
Environmental Health Scientist
Methods Section (OS-331)
cc: David Bussard
Alec McBride
Steve Cochran
Mike Petruska
John Austin
Leon Lazarus, Region II
Hugh Davis, OWPE
RCRA/Superfund Hotline
MICE Line
6-14
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References
1. Code of Federal Regulations, Part 260, Office of the Federal Register National Archives
and Records Administration, Revised July, 1992.
2. Code of Federal Regulations, Part 261, Office of the Federal Register National Archives
and Records Administration, Revised July, 1992.
3. Code of Federal Regulations, Part 268, Office of the Federal Register National Archives
and Records Administration, Revised July, 1992.
4. U.S. EPA, Test Methods for Evaluating Solid Wastes, SW-846 Revision 1, November
1990.
5. U.S. EPA, Characterizing Heterogeneous Wastes: Methods and Recommendations.
EPA600/R-92/033. February 1992.
6. U.S. EPA, Contract Laboratory Program Statement of Work for Inorganics Analysis,
Document Number ILM01,1991.
7. U.S. EPA, Contract Laboratory Program Statement of Work for Organics Analysis,
Document Number OLM01.8, June 1991.
8. U.S. EPA, Contract Laboratory Program, National Functional Guidelines for Organic
Data Review, June 1991.
9. U.S. EPA, Laboratory Data Validation Functional Guidelines for Evaluating Inorganic
Analysis, July 1, 1988.
10. U.S. EPA Region II, Training Course for CLP Organic Data Validation, Draft June 1992.
11. U.S. EPA Region II, CERCLA Quality Assurance Manual, March 1988.
12. Dr. Larry Jackson, Guidelines for the Conduct of the Toxicity Characteristic Leaching
Procedure, Associated Design and Manufacturing Co., September 1, 1992
13. U.S. EPA Workshop on Predicting the Environmental Impact of Oily Materials, Eghth
Annual Waste Testing and QA Symposium, July 14,1992.
14. U.S. EPA, Leachability Phenomena Recommendations and Rationale for Analysis of
Contaminant Release by the Environmental Engineering Committee, October 1991.
15. U.S. EPA Region II, Selected QA Issues of TCLP, July 1991.
16. U.S. EPA Office of Solid Waste and Office of Environmental Guidance Environment,
Safety and Health, U.S. DOE and Oak Ridge Associated University, Toxicity
Characteristic Training Course, February 7,1991.
17. U.S. EPA Region II, TCLP Data Validation, Standard Operating Procedure HW-7
Revision 1, March 1992.
18. Neptune, Dean, Moorehead, A.L., Michael, D.I., Streamlining Superfund Soil Studies:
Using the Data Quality Objectives Process For Scoping
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Appendix I
TCLP Methods From
40 CFR 261 Appendix II
SW 846 Method 1311
(Method Without Typographical Errors)
July 1992
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METHOD 1311
TOXICITY CHARACTERISTIC LEACHING PROCEDURE
1.0 SCOPE AND APPLICATION
1.1 The TCLP is designed to determine the mobility of both organic and
inorganic analytes present in liquid, solid, and multiphasic wastes.
1.2 If a total analysis of the waste demonstrates that individual
analytes are not present in the waste, or that they are present but at such low
concentrations that the appropriate regulatory levels could not possibly be
exceeded, the TCLP need not be run.
1.3 If an analysis of any one of the liquid fractions of the TCLP
extract indicates that a regulated compound is present at such high concentra-
tions that, even after accounting for dilution from the other fractions of the
extract, the concentration would be above the regulatory level for that compound,
then the waste is hazardous and it is not necessary to analyze the remaining
fractions of the extract.
1.4 If an analysis of extract obtained using a bottle extractor shows
that the concentration of any regulated volatile analyte exceeds the regulatory
level for that compound, then the waste is hazardous and extraction using the ZHE
is not necessary. However, extract from a bottle extractor cannot be used to
demonstrate that the concentration of volatile compounds is below the regulatory
level.
2.0 SUMMARY OF METHOD
2.1 For liquid wastes (i.e.. those containing less than 0.5% dry solid
material), the waste, after filtration through a 0.6 to 0.8 urn glass fiber
filter, is defined as the TCLP extract.
2.2 For wastes containing greater than or equal to 0.5% solids, the
liquid, if any, is separated from the solid phase and stored for later analysis;
the particle size of the solid phase is reduced, if necessary. The solid phase
is extracted with an amount of extraction fluid equal to 20 times the weight of
the solid phase. The extraction fluid employed is a function of the alkalinity
of the solid phase of the waste. A special extractor vessel is used when testing
for volatile analytes (see Table 1 for a list of volatile compounds). Following
extraction, the liquid extract is separated from the solid phase by filtration
through a 0.6 to 0.8 /xm glass fiber filter.
2.3 If compatible (i.e., multiple phases will not form on combination),
the initial liquid phase of the waste is added to the liquid extract, and these
are analyzed together. If incompatible, the liquids are analyzed separately and
the results are mathematically combined to yield a volume-weighted average
concentration.
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3.0 INTERFERENCES
3.1 Potential interferences that may be encountered during analysis are
discussed in the individual analytical methods.
4.0 APPARATUS AND MATERIALS
4.1 Agitation apparatus: The agitation apparatus must be capable of
rotating the extraction vessel in an end-over-end fashion (see Figure 1) at
30 + 2 rpm. Suitable devices known to EPA are identified in Table 2.
4.2 Extraction Vessels
4.2.1 Zero-Headspace Extraction Vessel (ZHE). This device is
for use only when the waste is being tested for the mobility of volatile
analytes M.e., those listed in Table 1). The ZHE (depicted in Figure 2)
allows for liquid/solid separation within the device, and effectively
precludes headspace. This type of vessel allows for initial liquid/solid
separation, extraction, and final extract filtration without opening the
vessel (see Section 4.3.1). The vessels shall have an internal volume of
500-600 mL, and be equipped to accommodate a 90-110 mm filter. The devices
contain VITON"1 0-rings which should be replaced frequently. Suitable ZHE
devices known to EPA are identified in Table 3.
For the ZHE to be acceptable for use, the piston within the ZHE
should be able to be moved with approximately 15 psi or less. If it takes
more pressure to move the piston, the 0-rings in the device should be
replaced. If this does not solve the problem, the ZHE is unacceptable for
TCLP analyses and the manufacturer should be contacted.
The ZHE should be checked for leaks after every extraction. If the
device contains a built-in pressure gauge, pressurize the device to
50 psi, allow it to stand unattended for 1 hour, and recheck the pressure.
If the device does not have a built-in pressure gauge, pressurize the
device to 50 psi, submerge it in water, and check for the presence of air
bubbles escaping from any of the fittings. If pressure is lost, check all
fittings and inspect and replace 0-rings, if necessary. Retest the
device. If leakage problems cannot be solved, the manufacturer should be
contacted.
Some ZHEs use gas pressure to actuate the ZHE piston, while others
use mechanical pressure (see Table 3). Whereas the volatiles procedure
(see Section 7.3) refers to pounds per square inch (psi), for the
mechanically actuated piston, the pressure applied is measured in
torque-inch-pounds. Refer to the manufacturer's instructions as to the
proper conversion.
1 VITON* is a trademark of Du Pont.
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4.2.2 Bottle Extraction Vessel. When the waste is being
evaluated using the nonvolatile extraction, a jar with sufficient capacity
to hold the sample and the extraction fluid is needed. Headspace is
allowed in this vessel.
The extraction bottles may be constructed from various materials,
depending on the analytes to be analyzed and the nature of the waste (see
Section 4.3.3). It is recommended that borosilicate glass bottles be used
instead of other types of glass, especially when inorganics are of
concern. Plastic bottles, other than polytetrafluoroethylene, shall not
be used if organics are to be investigated. Bottles are available from a
number of laboratory suppliers. When this type of extraction vessel is
used, the filtration device discussed in Section 4.3.2 is used for initial
liquid/solid separation and final extract filtration.
4.3 Filtration Devices: It is recommended that all filtrations be
performed in a hood.
4.3.1 Zero-Headspace Extractor Vessel (ZHE): When the waste is
evaluated for volatiles, the zero-headspace extraction vessel described in
Section 4.2.1 is used for filtration. The device shall be capable of
supporting and keeping in place the glass fiber filter and be able to
withstand the pressure needed to accomplish .separation (50 psi).
NOTE: When it is suspected that the glass fiber filter has been ruptured,
an in-line glass fiber filter may be used to filter the material
within the ZHE.
4.3.2 Filter Holder: When the waste is evaluated for other than
volatile analytes, any filter holder capable of supporting a glass fiber
filter and able to withstand the pressure needed to accomplish separation
may be used. Suitable filter holders range from simple vacuum units to
relatively complex systems capable of exerting pressures of up to 50 psi
or more. The type of filter holder used depends on the properties of the
material to be filtered (see Section 4.3.3). These devices shall have a
minimum internal volume of 300 ml and be equipped to accommodate a minimum
filter size of 47 mm (filter holders having an internal capacity of 1.5 L
or greater, and equipped to accommodate a 142 mm diameter filter, are
recommended). Vacuum filtration can only be used for wastes with low
solids content (<10%) and for highly granular, liquid-containing wastes.
All other types of wastes should be filtered using positive pressure
filtration. Suitable filter holders known to EPA are shown in Table 4.
4.3.3 Materials of Construction: Extraction vessels and
filtration devices shall be made of inert materials which will not leach
or absorb waste components. Glass, polytetrafluoroethylene (PTFE), or
type 316 stainless steel equipment may be used when evaluating the
mobility of both organic and inorganic components. Devices made of high
density polyethylene (HOPE), polypropylene (PP), or polyvinyl chloride
(PVC) may be used only when evaluating the mobility of metals. Borosili-
cate glass bottles are recommended for use over other types of glass
bottles, especially when inorganics are analytes of concern.
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4.4 Filters: Filters shall be made of borosilicate glass fiber, shall
contain no binder materials, and shall have an effective pore size of 0.6 to
0.8 /im, or equivalent. Filters known to EPA which meet these specifications are
identified in Table 5. Pre-filters must not be used. When evaluating the
mobility of metals, filters shall be acid-washed prior to use by rinsing with IN
nitric acid followed by three consecutive rinses with deionized distilled water
(a minimum of 1 L per rinse is recommended). Glass fiber filters are fragile and
should be handled with care.
4.5 pH Meters: The meter should be accurate to ± 0.05 units at 25 °C.
4.6 ZHE Extract Collection Devices: TEDLAR*2 bags or glass, stainless
steel or PTFE gas-tight syringes are used to collect the initial liquid phase and
the final extract of the waste when using the ZHE device. The devices listed are
recommended for use under the following conditions:
4.6.1 If a waste contains an aqueous liquid phase or if a waste
does not contain a significant amount of nonaqueous liquid (i .e., <1% of
total waste), the TEDLAR* bag or a 600 ml syringe should be used to collect
and combine the initial liquid and solid extract.
4.6.2 If a waste contains a significant amount of nonaqueous
liquid in thee initial liquid phase (i.e., >1% of total waste), the syringe
or the TEDLAR* bag may be used for both the initial solid/liquid separation
and the final extract filtration. However, analysts should use one or the
other, not both.
4.6.3 If the waste contains no initial liquid phase (is 100%
solid)^or has no significant solid phase (is 100% liquid), either the
TEDLAR* bag or the syringe may be used. If the syringe is used, discard
the first 5 mL of liquid expressed from the device. The remaining
aliquots are used for analysis.
4.7 ZHE Extraction Fluid Transfer Devices: Any device capable of
transferring the extraction fluid into the ZHE without changing the nature of the
extraction fluid is acceptable (e.g., a positive displacement or peristaltic
pump, a gas tight syringe, pressure filtration unit (see Section 4.3.2), or other
ZHE device).
4.8 Laboratory Balance: Any laboratory balance accurate to within
+ 0.01 grams may be used (all weight measurements are to be within + 0.1 grams).
flask.
4.9 Beaker or Erlenmeyer flask, glass, 500 mL.
4.10 Watchglass, appropriate diameter to cover beaker or Erlenmeyer
TEDLAR8 is a registered trademark of Du Pont.
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4.11 Magnetic stirrer.
5.0 REAGENTS
5.1 Reagent grade chemicals shall be used in all tests. Unless
otherwise indicated, it is intended that all reagents shall conform to the
specifications of the Committee on Analytical Reagents of the American Chemical
Society, where such specifications are available. Other grades may be used,
provided it is first ascertained that the reagent is of sufficiently high purity
to permit its use without lessening the accuracy of the determination.
5.2 Reagent Water. Reagent water is defined as water in which an
interferant is not observed at or above the method's detection limit of the
analyte(s) of interest. For nonvolatile extractions, ASTM Type II water or
equivalent meets the definition of reagent water. For volatile extractions, it
is recommended that reagent water be generated by any of the following methods.
Reagent water should be monitored periodically for impurities.
5.2.1 Reagent water for volatile extractions may be generated
by passing tap water through a carbon filter bed containing about 500
grams of activated carbon (Calgon Corp., Filtrasorb-300 or equivalent).
5.2.2 A water purification system (Millipore Super-Q or
equivalent) may also be used to generate reagent water for volatile
extractions.
5.2.3 Reagent water for volatile extractions may also be
prepared by boiling water for 15 minutes. Subsequently, while maintaining
the water temperature at 90 + 5 degrees C, bubble a contaminant-free inert
gas (e.g. nitrogen) through the water for 1 hour. While still hot,
transfer the water to a narrow mouth screw-cap bottle under zero-headspace
and seal with a Teflon-lined septum and cap.
5.3 Hydrochloric acid (IN), HC1, made from ACS reagent grade.
5.4 Nitric acid (IN), HN03, made from ACS reagent grade.
5.5 Sodium hydroxide (IN), NaOH, made from ACS reagent grade.
5.6 Glacial acetic acid, CH3CH2OOH, ACS reagent grade.
5.7 Extraction fluid.
5.7.1 Extraction fluid # 1: Add 5.7 ml glacial CH3CH2OOH to
500 mL of reagent water (See Section 5.2), add 64.3 ml of IN NaOH, and
dilute to a volume of 1 liter. When correctly prepared, the pH of this
fluid will be 4.93 + 0.05.
5.7.2 Extraction fluid $ 2: Dilute 5.7 ml glacial CH3CH2OOH with
reagent water (See Section 5.2) to a volume of 1 liter. When correctly
prepared, the pH of this fluid will be 2.88 + 0.05.
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NOTE: These extraction fluids should be monitored frequently for
impurities. The pH should be checked prior to use to ensure that
these fluids are made up accurately. If impurities are found or
the pH is not within the above specifications, the fluid shall be
discarded and fresh extraction fluid prepared.
5.8 Analytical standards shall be prepared according to the appropriate
analytical method.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 All samples shall be collected using an appropriate sampling plan.
6.2 The TCLP may place requirements on the minimal size of the field
sample, depending-upon the physical state or states of the waste and the analytes
of concern. An aliquot is needed for preliminary evaluation of which extraction
fluid is to be used for the nonvolatile analyte extraction procedure. Another
aliquot may be needed to actually conduct the nonvolatile extraction (see Section
1.4 concerning the use of this extract for volatile organics). If volatile
organics are of concern, another aliquot may be needed. Quality control measures
may require additional aliquots. Further, it is always wise to collect more
sample just in case something goes wrong with the initial attempt to conduct the
test.
6.3 Preservatives shall not be added to samples before extraction.
6.4 Samples may be refrigerated unless refrigeration results in
irreversible physical change to the waste. If precipitation occurs, the entire
sample (including precipitate) should be extracted.
6.5 When the waste is to be evaluated for volatile analytes, care shall
be taken to minimize the loss of volatiles. Samples shall be collected and
stored in a manner intended to prevent the loss of volatile analytes (e.g.,
samples should be collected in Teflon-lined septum capped vials and stored at 4
*C. Samples should be opened only immediately prior to extraction).
6.6 TCLP extracts should be prepared for analysis and analyzed as soon
as possible following extraction. Extracts or portions of extracts for metallic
analyte determinations must be acidified with nitric acid to a pH < 2, unless
precipitation occurs (see Section 7.2.14 if precipitation occurs). Extracts
should be preserved for other analytes according to the guidance given in the
individual analysis methods. Extracts or portions of extracts for organic
analyte determinations shall not be allowed to come into contact with the
atmosphere (i.e., no headspace) to prevent losses. See Section 8.0 (QA
requirements) for acceptable sample and extract holding times.
7.0 PROCEDURE
7.1 Preliminary Evaluations
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Perform preliminary TCLP evaluations on a minimum 100 gram aliquot of
waste. This aliquot may not actually undergo TCLP extraction. These preliminary
evaluations include: (1) determination of the percent solids (Section 7.1.1);
(2) determination of whether the waste contains insignificant solids and is,
therefore, its own extract after filtration {Section 7.1.2); (3) determination
of whether the solid portion of the waste requires particle size reduction
(Section 7.1.3); and (4) determination of which of the two extraction fluids are
to be used for the nonvolatile TCLP extraction of the waste (Section 7.1.4).
7.1.1 Preliminary determination of percent solids: Percent
solids is defined as that fraction of a waste sample (as a percentage of
the total sample) from which no liquid may be forced out by an applied
pressure, as described below.
7.1.1.1 If the waste will obviously yield no liquid when
subjected to pressure filtration (i.e.. is 100% solids) proceed to
Section 7.1.3.
7.1.1.2 If the sample is liquid or multiphasic,
liquid/solid separation to make a preliminary determination of
percent solids is required. This involves the filtration device
described in Section 4.3.2 and is outlined in Sections 7.1.1.3
through 7.1.1.9.
7.1.1.3 Pre-weigh the filter and the container that will
receive the filtrate.
7.1.1.4 Assemble the filter holder and filter following
the manufacturer's instructions. Place the filter on the support
screen and secure.
7.1.1.5 Weigh out a subsample of the waste (100 gram
minimum) and record the weight.
7.1.1.6 Allow slurries to stand to permit the solid
phase to settle. Wastes that settle slowly may be centrifuged
prior to filtration. Centrifugation is to be used only as an aid
to filtration. If used, the liquid should be decanted and filtered
followed by filtration of the solid portion of the -waste through
the same filtration system.
7.1.1.7 Quantitatively transfer the waste sample to the
filter holder (liquid and solid phases). Spread the waste sample
evenly over the surface of the filter. If filtration of the waste
at 4 °C reduces the amount of expressed liquid over what would be
expressed at room temperature then allow the sample to warm up to
room temperature in the device before filtering.
NOTE: If waste material (>1% of original sample weight) has obviously
adhered to the container used to transfer the sample to the
filtration apparatus, determine the weight of this residue and
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subtract it from the sample weight determined in Section 7.1.1.5 to
determine the weight of the waste sample that will be filtered.
Gradually apply vacuum or gentle pressure of 1-10 psi,
until air or pressurizing gas moves through the filter. If this
point is not reached under 10 psi, and if no additional liquid has
passed through the filter in any 2 minute interval, slowly increase
the pressure in 10 psi increments to a maximum of 50 psi. After
each incremental increase of 10 psi, if the pressurizing gas has
not moved through the filter, and if no additional liquid has
passed through the filter in any 2 minute interval, proceed to the
next 10 psi increment. When the pressurizing gas begins to move
through the filter, or when liquid flow has ceased at 50 psi (i.e.,
filtration does not result in any additional filtrate within any 2
minute period), stop the filtration.
NOTE: Instantaneous application of high pressure can degrade the glass
fiber filter and may cause premature plugging.
7.1.1.8 The material in the filter holder is defined as
the solid phase of the waste, and the filtrate is defined as the
liquid phase.
NOTE: Some wastes, such as oily wastes and some paint wastes, will
obviously contain some material that appears to be a liquid. Even
after applying vacuum or pressure filtration, as outlined in
Section 7.1.1.7, this material may not filter. If this is the
case, the material within the filtration device is defined as a
solid. Do not replace the original filter with a fresh filter
under any circumstances. Use only one filter.
7.1.1.9 Determine the weight of the liquid phase by
subtracting the weight of the filtrate container (see Section
7.1.1.3) from the total weight of the filtrate-filled container.
Determine the weight of the solid phase of the waste sample by
subtracting the weight of the liquid phase from the weight of the
total waste sample, as determined in Section 7.1.1.5 or 7.1.1.7.
Record the weight of the liquid and solid phases.
Calculate the percent solids as follows:
Weight of solid (Section 7.1.1.9)
Percent solids = x 100
Total weight of waste (Section 7.1.1.5 or 7.1.1.7)
7.1.2 If the percent solids determined in Section 7.1.1.9 is
equal to or greater than 0.5%, then proceed either to Section 7.1.3 to
determine whether the solid material requires particle size reduction or
to Section 7.1.2.1 if it is noticed that a small amount of the filtrate is
entrained in wetting of the filter. If the percent solids determined in
Section 7.1.1.9 is less than 0.5%, then proceed to Section 7.2.9 if the
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nonvolatile TCLP is to be performed and to Section 7.3 with a fresh
portion of the waste if the volatile TCLP is to be performed.
7.1.2.1 Remove the solid phase and filter from the
filtration apparatus.
7.1.2.2 Dry the filter and solid phase at 100 ± 20 eC
until two successive weighing yield the same value within ± 1%.
Record the final weight.
NOTE: Caution should be taken to ensure that the subject solid will not
flash upon heating. It is recommended that the drying oven be
vented to a hood or other appropriate device.
7.1.2.3 Calculate the percent dry solids as follows:
(Wt. of dry waste + filter) - tared wt. of filter
Percent dry solids = — x 100
Initial wt. of waste (Section 7.1.1.5 or 7.1.1.7)
7.1.2.4 If the percent dry solids is less than 0.5%,
then proceed to Section 7.2.9 if the nonvolatile TCLP is to be
performed, and to Section 7.3 if the volatile TCLP is to be
performed. If the percent dry solids is greater than or equal to
0.5%, and if the nonvolatile TCLP is to be performed, return to the
beginning of this Section (7.1) and, with a fresh portion of waste,
determine whether particle size reduction is necessary (Section
7.1.3) and determine the appropriate extraction fluid (Section
7.1.4). If only the volatile TCLP is to be performed, see the note
in Section 7.1.4.
7.1.3 Determination of whether the waste requires particle size
reduction (particle size is reduced during this step): Using the solid
portion of the waste, evaluate the solid for particle size. Particle size
reduction is required, unless the solid has a surface area per gram of
material equal to or greater than 3.1 cm2, or is smaller than 1 cm in its
narrowest dimension (i .e., is capable of passing through a 9.5 mm (0.375
inch) standard sieve). If the surface area is smaller or the particle
size larger than described above, prepare the solid portion of the waste
for extraction by crushing, cutting, or grinding the waste to a surface
area or particle size as described above. If the solids are prepared for
organic volatiles extraction, special precautions must be taken (see
Section 7.3.6).
NOTE: Surface area criteria are meant for filamentous (e.g., paper, cloth, and
similar) waste materials. Actual measurement of surface area is not
required, nor is it recommended. For materials that do not obviously meet
the criteria, sample specific methods would need to be developed and
employed to measure the surface area. Such methodology is currently not
available.
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7.1.4 Determination of appropriate extraction fluid: If the
solid content of the waste is greater than or equal to 0.5% and if the
sample will be extracted for nonvolatile constituents (Section 7.2),
determine the appropriate fluid (Section 5.7) for the nonvolatiles
extraction as follows:
NOTE: TCLP extraction for volatile constituents uses only extraction
fluid #1 (Section 5.7.1). Therefore, if TCLP extraction for
nonvolatiles is not required, proceed to Section 7.3.
7.1.4.1 Weigh out a small subsample of the solid phase
of the waste, reduce the solid (if necessary) to a particle size of
approximately 1 mm in diameter or less, and transfer 5.0 grams of
the solid phase of the waste to a 500 ml beaker or Erlenmeyer
flask.
7.1.4.2 Add 96.5 ml of reagent water to the beaker,
cover with a watchglass, and stir vigorously for 5 minutes using a
magnetic stirrer. Measure and record the pH. If the pH is <5.0,
use extraction fluid #1. Proceed to Section 7.2.
7.1.4.3 If the pH from Section 7.1.4.2 is >5.0, add
3.5 mL IN HC1, slurry briefly, cover with a watchglass, heat to 50
*C, and hold at 50 °C for 10 minutes.
7.1.4.4 Let the solution cool to room temperature and
record the pH. If the pH is <5.0, use extraction fluid #1. If the
pH is >5.0, use extraction fluid #2. Proceed to Section 7.2.
7.1.5 If the aliquot of the waste used for the preliminary
evaluation (Sections 7.1.1 - 7.1.4) was determined to be 100% solid at
Section 7.1.1.1, then it can be used for the Section 7.2 extraction
(assuming at least 100 grams remain), and the Section 7.3 extraction
(assuming at least 25 grams remain). If the aliquot was subjected to the
procedure in Section 7.1.1.7, then another aliquot shall be used for the
volatile extraction procedure in Section 7.3. The aliquot of the waste
subjected to the procedure in Section 7.1.1.7 might be appropriate for use
for the Section 7.2 extraction if an adequate amount of solid (as
determined by Section 7.1.1.9) was obtained. The amount of solid
necessary is dependent upon whether a sufficient amount of extract will be
produced to support the analyses. If an adequate amount of solid remains,
proceed to Section 7.2.10 of the nonvolatile TCLP extraction.
7.2 Procedure When Volatiles are not Involved
A minimum sample size of 100 grams (solid and liquid phases) is recommend-
ed. In some cases, a larger sample size may be appropriate, depending on the
solids content of the waste sample (percent solids, See Section 7.1.1), whether
the initial liquid phase of the waste will be miscible with the aqueous extract
of the solid, and whether inorganics, semivolatile organics, pesticides, and
herbicides are all analytes of concern. Enough solids should be generated for
extraction such that the volume of TCLP extract will be sufficient to support all
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of the analyses required. If the amount of extract generated by a single TCLP
extraction will not be sufficient to perform all of the analyses, more than one
extraction may be performed and the extracts from each combined and aliquoted for
analysis.
7.2.1 If the waste will obviously yield no liquid when subjected
to pressure filtration (i.e., is 100% solid, see Section 7.1.1), weigh out
a subsample of the waste (100 gram minimum) and proceed to Section 7.2.9.
7.2.2 If the sample is liquid or multiphasic, liquid/solid
separation is required. This involves the filtration device described in
Section 4.3.2 and is outlined in Sections 7.2.3 to 7.2.8.
7.2.3 Pre-weigh the container that will receive the filtrate.
7.2.4 Assemble the filter holder and filter following the
manufacturer's instructions. Place the filter on the support screen and
secure. Acid wash the filter if evaluating the mobility of metals (see
Section 4.4).
NOTE: Acid washed filters may be used for all nonvolatile extractions
even when metals are not of concern.
7.2.5 Weigh out a subsample of the waste (100 gram minimum) and
record the weight. If the waste contains <0.5% dry solids (Section
7.1.2), the liquid portion of the waste, after filtration, is defined as
the TCLP extract. Therefore, enough of the sample should be filtered so
that the amount of filtered liquid will support all of the analyses
required of the TCLP extract. For wastes containing >0.5% dry solids
(Sections 7.1.1 or 7.1.2), use the percent solids information obtained in
Section 7.1.1 to determine the optimum sample size (100 gram minimum) for
filtration. Enough solids should be generated by filtration to support
the analyses to be performed on the TCLP extract.
7.2.6 Allow slurries to stand to permit the solid phase to
settle. Wastes that settle slowly may be centrifuged prior to filtration.
Use centrifugation only as an aid to filtration. If the waste is
centrifuged, the liquid should be decanted and filtered followed by
filtration of the solid portion of the waste through the same filtration
system.
7.2.7 Quantitatively transfer the waste sample (liquid and solid
phases) to the filter holder (see Section 4.3.2). Spread the waste sample
evenly over the surface of the filter. If filtration of the waste at 4 "C
reduces the amount of expressed liquid over what would be expressed at
room temperature, then allow the' sample to warm up to room temperature in
the device before filtering.
NOTE: If waste material (>1% of the original sample weight) has obviously
adhered to the container used to transfer the sample to the
filtration apparatus, determine the weight of this residue and
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subtract it from the sample weight determined in Section 7.2.5, to
determine the weight of the waste sample that will be filtered.
Gradually apply vacuum or gentle pressure of 1-10 psi, until air or
pressurizing gas moves through the filter. If this point is not reached
under 10 psi, and if no additional liquid has passed through the filter in
any 2 minute interval, slowly increase the pressure in 10 psi increments
to a maximum of 50 psi. After each incremental increase of 10 psi, if the
pressurizing gas has not moved through the filter, and if no additional
liquid has passed through the filter in any 2 minute interval, proceed to
the next 10 psi increment. When the pressurizing gas begins to move
through the filter, or when the liquid flow has ceased at 50 psi (i.e.,
filtration does not result in any additional filtrate within a 2 minute
period), stop the filtration.
NOTE: Instantaneous application of high pressure can degrade the glass
fiber filter and may cause premature plugging.
7.2.8 The material in the filter holder is defined as the solid
phase of the waste, and the filtrate is defined as the liquid phase.
Weigh the filtrate. The liquid phase may now be either analyzed (See
Section 7.2.12) or stored at 4 °C until time of analysis.
NOTE: Some wastes, such as oily wastes and some paint wastes, will
obviously contain some material that appears to be a liquid. Even
after applying vacuum or pressure filtration, as outlined in
Section 7.2.7, this material may not filter. If this is the case,
the material within the filtration device is defined as a solid and
is carried through the extraction as a solid. Do not replace the
original filter with a fresh filter under any circumstances. Use
only one filter.
7.2.9 If the waste contains <0.5% dry solids (see Section
7.1.2), proceed to Section 7.2.13. If the waste contains >0.5% dry solids
(see Section 7.1.1 or 7.1.2), and if particle size reduction of the solid
was needed in Section 7.1.3, proceed to Section 7.2.10. If the waste as
received passes a 9.5 mm sieve, quantitatively transfer the solid material
into the extractor bottle along with the filter used to separate the
initial liquid from the solid phase, and proceed to Section 7.2.11.
7.2.10 Prepare the solid portion of the waste for extraction by
crushing, cutting, or grinding the waste to a surface area or particle
size as described in Section 7.1.3. When the surface area or particle
size has been appropriately altered, quantitatively transfer the solid
material into an extractor bottle. .Include the filter used to separate the
initial liquid from the solid phase.
NOTE: Sieving of the waste is not normally required. Surface area
requirements are meant for filamentous (e.g., paper, cloth) and
similar waste materials. Actual measurement of surface area is not
recommended. If sieving is necessary, a Teflon coated sieve should
be used to avoid contamination of the sample.
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7.2.11 Determine the amount of extraction fluid to add to the
extractor vessel as follows:
20 x percent solids (Section 7.1.1) x weight of waste
filtered (Section 7.2.5 or 7.2.7)
Weight of =
extraction fluid 100
Slowly add this amount of appropriate extraction fluid (see Section
7.1.4) to the extractor vessel. Close the extractor bottle tightly (it is
recommended that Teflon tape be used to ensure a tight seal), secure in
rotary agitation device, and rotate at 30 + 2 rpm for 18 + 2 hours.
Ambient temperature (i.e., temperature of room in which extraction takes
place) shall be maintained at 23 ±.2 'C during the extraction period.
NOTE: As agitation continues, pressure may build up within the extractor
bottle for some types of wastes (e.g., limed or calcium carbonate
containing waste may evolve gases such as carbon dioxide). To
relieve excess pressure, the extractor bottle may be periodically
opened (e.g., after 15 minutes, 30 minutes, and 1 hour) and vented
into a hood.
7.2.12 Following the 18 + 2 hour extraction, separate the
material in the extractor vessel into its component liquid and solid
phases by filtering through a new glass fiber filter, as outlined in
Section 7.2.7. For final filtration of the TCLP extract, the glass fiber
filter may be changed, if necessary, to facilitate filtration. Filter(s)
shall be acid-washed (see Section 4.4) if evaluating the mobility of
metals.
7.2.13 Prepare the TCLP extract as follows:
7.2.13.1 If the waste contained no initial liquid
phase, the filtered liquid material obtained from Section 7.2.12 is
defined as the TCLP extract. Proceed to Section 7.2.14.
7.2.13.2 If compatible (e.g., multiple phases will not
result on combination), combine the filtered liquid resulting from
Section 7.2.12 with the initial liquid phase of the waste obtained
in Section 7.2.7. This combined liquid is defined as the TCLP
extract. Proceed to Section 7.2.14.
7.2.13.3 If the initial liquid phase of the waste, as
obtained from Section 7.2.7, is not or may not be compatible with
the filtered liquid resulting from Section 7.2.12, do not combine
these liquids. Analyze these liquids, collectively defined as the
TCLP extract, and combine the results mathematically, as described
in Section 7.2.14.
7.2.14 Following collection of the TCLP extract, the pH of the
extract should be recorded. Immediately aliquot and preserve the extract
for analysis. Metals aliquots must be acidified with nitric acid to
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pH <2. If precipitation is observed upon addition of nitric acid to a
small aliquot of the extract, then the remaining portion of the extract
for metals analyses shall not be acidified and the extract shall be
analyzed as soon as possible. All other aliquots must be stored under
refrigeration (4 °C) until analyzed. The TCLP extract shall be prepared
and analyzed according to appropriate analytical methods. TCLP extracts to
be analyzed for metals shall be acid digested except in those instances
where digestion causes loss of metallic analytes. If an analysis of the
undigested extract shows that the concentration of any regulated metallic
analyte exceeds the regulatory level, then the waste is hazardous and
digestion of the extract is not necessary. However, data on undigested
extracts alone cannot be used to demonstrate that the waste is not
hazardous. If the individual phases are to be analyzed separately,
determine the volume of the individual phases (to ± 0.5%), conduct the
appropriate analyses, and .combine the results mathematically by using a
simple volume-weighted average:
(V,) (C,) + (V2) (C2)
Final Analyte Concentration =
V, + V2
where:
V, = The volume of the first phase (L).
C, = The concentration of the analyte of concern in the first phase (mg/L).
V2 = The volume of the second phase (L).
C2 = The concentration of the analyte of concern in the second phase
(mg/L).
7.2.15 Compare the analyte concentrations in the TCLP extract
with the levels identified in the appropriate regulations. Refer to
Section 8.0 for quality assurance requirements.
7.3 Procedure When Volatiles are Involved
Use the ZHE device to obtain TCLP extract for analysis of volatile
compounds only. . Extract resulting from the use of the ZHE shall not be used to
evaluate the mobility of nonvolatile analytes (e.g., metals, pesticides, etc.).
The ZHE device has approximately a 500 mL internal capacity. The ZHE can
thus accommodate a maximum of 25 grams of solid (defined as that fraction of a
sample from which no additional liquid may be forced out by an applied pressure
of 50 psi), due to the need to add an amount of extraction fluid equal to 20
times the weight of the solid phase.
Charge the ZHE with sample only once and do not open the device until the
final extract (of the solid) has been collected. Repeated filling of the ZHE to
obtain 25 grams of solid is not permitted.
Do not allow the waste, the initial liquid phase, or the extract to be
exposed to the atmosphere for any more time than is absolutely necessary. Any
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manipulation of these materials should be done when cold (4 °C) to minimize loss
of volatiles.
7.3.1 Pre-weigh the (evacuated) filtrate collection container
(See Section 4.6) and set aside. If using a TEDLAR* bag, express all
liquid from the ZHE device into the bag, whether for the initial or final
liquid/solid separation, and take an aliquot from the liquid in the bag
for analysis. The containers listed in Section 4.6 are recommended for
use under the conditions stated in Sections 4.6.1 - 4.6.3.
7.3.2 Place the ZHE piston within the body of the ZHE (it may be
helpful first to moisten the piston 0-rings slightly with extraction
fluid). Adjust the piston within the ZHE body to a height that will
minimize the distance the piston will have to move once the ZHE is charged
with sample (based upon sample size requirements determined from Section
7.3, Section 7.1.1 and/or 7.1.2). Secure the gas inlet/outlet flange
(bottom flange) onto the ZHE body in accordance with the manufacturer's
instructions. Secure the glass fiber filter between the support screens
and set aside. Set liquid inlet/outlet flange (top flange) aside.
7.3.3 If the waste is 100% solid (see Section 7.1.1), weigh out
a subsample (25 gram maximum) of the waste, record weight, and proceed to
Section 7.3.5.
7.3.4 If the waste contains < 0.5% dry solids (Section 7.1.2),
the liquid portion of waste, after filtration, is defined as the TCLP
extract. Filter enough of the sample so that the amount of filtered
liquid will support all of the volatile analyses required. For wastes
containing > 0.5% dry solids (Sections 7.1.1 and/or 7.1.2), use the
percent solids information obtained in Section 7.1.1 to determine the
optimum sample size to charge into the ZHE. The recommended sample size
is as follows:
7.3.4.1 For wastes containing < 5% solids (see Section
7.1.1), weigh out a 500 gram subsample of waste and record the
weight.
7.3.4.2 For wastes containing > 5% solids (see Section
7.1.1), determine the amount of waste to charge into the ZHE as
fol 1ows:
25
Weight of waste to charge ZHE = x 100
percent solids (Section 7.1.1)
Weigh out a subsample of the waste of the appropriate size and
record the weight.
7.3.5 If particle size reduction of the solid portion of the
waste was required in Section 7.1.3, proceed to Section 7.3.6. If
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particle size reduction was not required in Section 7.1.3, proceed to
Section 7.3.7.
7.3.6 Prepare the waste for extraction by crushing, cutting, or
grinding the solid portion of the waste to a surface area or particle size
as described in Section 7.1.3. Wastes and appropriate reduction equipment
should be refrigerated, if possible, to 4 °C prior to particle size
reduction. The means used to effect particle size reduction must not
generate heat in and of itself. If reduction of the solid phase of the
waste is necessary, exposure of the waste to the atmosphere should be
avoided to the extent possible.
NOTE: Sieving of the waste is not recommended due to the possibility that
volatiles may be lost. The use of an appropriately graduated ruler
is recommended as an acceptable alternative. Surface area
requirements are meant for filamentous (e.g., paper, cloth) and
similar waste materials. Actual measurement of surface area is not
recommended.
When the surface area or particle size has been appropriately
altered, proceed to Section 7.3.7.
7.3.7 Waste slurries need not be allowed to stand to permit the
solid phase to settle. Do not centrifuge wastes prior to filtration.
7.3.8 Quantitatively transfer the entire sample (liquid and
solid phases) quickly to the ZHE. Secure the filter and support screens
onto the top flange of the device and secure the top flange to the ZHE
body in accordance with the manufacturer's instructions. Tighten all ZHE
fittings and place the device in the vertical position (gas inlet/outlet
flange on the bottom). Do not attach the extract collection device to the
top plate.
NOTE: If waste material (>1% of original sample weight) has obviously
adhered to the container used to transfer the sample to the ZHE,
determine the weight of this residue and subtract it from the
sample weight determined in Section 7.3.4 to determine the weight
of the waste sample that will be filtered.
Attach a gas line to the gas inlet/outlet valve (bottom flange)
and, with the liquid inlet/outlet valve (top flange) open, begin applying
gentle pressure of 1-10 psi (or more if necessary) to force all headspace
slowly out of the ZHE device into a hood. At the first appearance of
liquid from the liquid inlet/outlet valve, quickly close the valve and
discontinue pressure. If filtration of the waste at 4 "C reduces the
amount of expressed liquid over what would be expressed at room tempera-
ture, then allow the sample to warm up to room temperature in the device
before filtering. If the waste is 100% solid (see Section 7.1.1), slowly
increase the pressure to a maximum of 50 psi to force most of the
headspace out of the device and proceed to Section 7.3.12.
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7.3.9 Attach the evacuated pre-weighed filtrate collection
container to the liquid inlet/outlet valve and open the valve. Begin
applying gentle pressure of 1-10 psi to force the liquid phase of the
sample into the filtrate collection container. If no additional liquid
has passed through the filter in any 2 minute interval, slowly increase
the pressure in 10 psi increments to a maximum of 50 psi. After each
incremental increase of 10 psi, if no additional liquid has passed through
the filter in any 2 minute interval, proceed to the next 10 psi increment.
When liquid flow has ceased such that continued pressure filtration at 50
psi does not result in any additional filtrate within a 2 minute period,
stop the filtration. Close the liquid inlet/outlet valve, discontinue
pressure to the piston, and disconnect and weigh the filtrate collection
container.
NOTE: Instantaneous application of high pressure can degrade the glass
fiber filter and may cause premature plugging.
7.3.10 The material in the ZHE is defined as the solid phase of
the waste and the filtrate is defined as the liquid phase.
NOTE: Some wastes, such as oily wastes and some paint wastes, will
obviously contain some material that appears to be a liquid. Even
after applying pressure filtration, this material will not filter.
If this is the case, the material within the filtration device is
defined as a solid and is carried through the TCLP extraction as a
solid.
If the original waste contained <0.5% dry solids (see Section
7.1.2), this filtrate is defined as the TCLP extract and is analyzed
directly. Proceed to Section 7.3.15.
7.3.11 The liquid phase may now be either analyzed immediately
(See Sections 7.3.13 through 7.3.15) or stored at 4 "C under minimal
headspace conditions until time of analysis. Determine the weight of
extraction fluid #1 to add to the ZHE as follows:
20 x percent solids (Section 7.1.1) x weight
of waste filtered (Section 7.3.4 or 7.3.8)
Weight of extraction fluid =
100
7.3.12 The following Sections detail how to add the appropriate
amount of extraction fluid to the solid material within the ZHE and
agitation of the ZHE vessel. Extraction fluid #1 is used in all cases
(See Section 5.7).
7.3.12.1 With the ZHE in the vertical position, attach
a line from the extraction fluid reservoir to the liquid in-
let/outlet valve. The line used shall contain fresh extraction
fluid and should be preflushed with fluid to eliminate any air
pockets in the line. Release gas pressure on the ZHE piston (from
the gas inlet/outlet valve), open the liquid inlet/outlet valve,
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and begin transferring extraction fluid (by pumping or similar
means) into the ZHE. Continue pumping extraction fluid into the
ZHE until the appropriate amount of fluid has been introduced into
the device.
7.3.12.2 After the extraction fluid has been added,
immediately close the liquid inlet/outlet valve and disconnect the
extraction fluid line. Check the ZHE to ensure that all valves are
in their closed positions. Manually rotate the device in an
end-over-end fashion 2 or 3 times. Reposition the ZHE in the
vertical position with the liquid inlet/outlet valve on top.
Pressurize the ZHE to 5-10 psi (if necessary) and slowly open the
liquid inlet/outlet valve to bleed out any headspace (into a hood)
that may have been introduced due to the addition of extraction
fluid. This bleeding shall be done quickly and shall be stopped at
the first appearance of liquid from the valve. Re-pressurize the
ZHE with 5-10 psi and check all ZHE fittings to ensure that they
are closed.
7.3.12.3 Place the ZHE in the rotary agitation appara-
tus (if it is not already there) and rotate at 30 ± 2 rpm for 18 ±
2 hours. Ambient temperature (i.e., temperature of room in which
extraction occurs) shall be maintained at 23 ± 2 "C during agita-
tion.
7.3.13 Following the 18+2 hour agitation period, check the
pressure behind the ZHE piston by quickly opening and closing the gas
inlet/outlet valve and noting the escape of gas. If the pressure has not
been maintained (i.e., no gas release observed), the device is leaking.
Check the ZHE for leaking as specified in Section 4.2.1, and perform the
extraction again with a new sample of waste. If the pressure within the
device has been maintained, the material in the extractor vessel is once
again separated into its component liquid and solid phases. If the waste
contained an initial liquid phase, the liquid may be filtered directly
into the same filtrate collection container (i .e., TEDLAR* bag) holding the
initial liquid phase of the waste. A separate filtrate collection
container must be used if combining would create multiple phases, or there
is not enough volume left within the filtrate collection container.
Filter through the glass fiber filter, using the ZHE device as discussed
in Section 7.3.9. All extract shall be filtered and collected if the
TEDLAR* bag is used, if the extract is multiphasic, or if the waste
contained an initial liquid phase (see Sections 4.6 and 7.3.1).
NOTE: An in-line glass fiber filter may be used to filter the material
within the ZHE if it is suspected that the glass fiber filter has
been ruptured.
7.3.14 If the original waste contained no initial liquid phase,
the filtered liquid material obtained from Section 7.3.13 is defined as
the TCLP extract. If the waste contained an initial liquid phase, the
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filtered liquid material obtained from Section 7.3.13 and the initial
liquid phase (Section 7.3.9) are collectively defined as the TCLP extract.
7.3.15 Following collection of the TCLP extract, immediately
prepare the extract for analysis and store with minimal headspace at 4 *C
until analyzed. Analyze the TCLP extract according to the appropriate
analytical methods. If the individual phases are to be analyzed
separately (i.e., are not miscible), determine the volume of the
individual phases (to 0.5%), conduct the appropriate analyses, and combine
the results mathematically by using a simple volume-weighted average:
(V,) (C,) + (V2) (C2)
Final Analyte
Concentration V,+ V2
where:
V, = The volume of the first phases (L).
C, = The concentration of the analyte of concern in the first phase (mg/L).
V2 = The volume of the second phase (L).
C2 = The concentration of the analyte of concern in the second phase
(mg/L).
7.3.16 Compare the analyte concentrations in the TCLP extract
with the levels identified in the appropriate regulations. Refer to
Section 8.0 for quality assurance requirements.
8.0 QUALITY ASSURANCE
8.1 A minimum of one blank (using the same extraction fluid as used for
the samples) must be analyzed for every 20 extractions that have been conducted
in an extraction vessel.
8.2 A matrix spike shall be performed for each waste type (e.g.,
wastewater treatment sludge, contaminated soil, etc.) unless the result exceeds
the regulatory level and the data are being used solely to demonstrate that the
waste property exceeds the regulatory level. A minimum of one matrix spike must
be analyzed for each analytical batch. As a minimum, follow the matrix spike
addition guidance provided in each analytical method.
8.2.1 Matrix spikes are to be added after filtration of the TCLP
extract and before preservation. Matrix spikes should not be added prior
to TCLP extraction of the sample.
8.2.2 In most cases, matrix spikes should be added at a
concentration equivalent to the corresponding regulatory level. If the
analyte concentration is less than one half the regulatory level, the
spike concentration may be as low as one half of the analyte concentra-
tion, but may not be not less than five times the method detection limit.
In order to avoid differences in matrix effects, the matrix spikes must be
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added to the same nominal volume of TCLP extract as that which was
analyzed for the unspiked sample.
8.2.3 The purpose of the matrix spike is to monitor the
performance of the analytical methods used, and to determine whether
matrix interferences exist. Use of other internal calibration methods,
modification of the analytical methods, or use of alternate analytical
methods may be needed to accurately measure the analyte concentration in
the TCLP extract when the recovery of the matrix spike is below the
expected analytical method performance.
8.2.4 Matrix spike recoveries are calculated by the following
formula:
%R (%Recovery) = 100 (X, - XJ/K
where:
Xs = measured value for the spiked sample,
Xu = measured value for the unspiked sample, and
K = known value of the spike in the sample.
8.3 All quality control measures described in the appropriate analytical
methods shall be followed.
8.4 The use of internal calibration quantitation methods shall be
employed for a metallic contaminant if: (1) Recovery of the contaminant from the
TCLP extract is not at least 50% and the concentration does not exceed the
regulatory level, and (2) The concentration of the contaminant measured in the
extract is within 20% of the appropriate regulatory level.
8.4.1. The method of standard additions shall be employed as the
internal calibration quantitation method for each metallic contaminant.
8.4.2 The method of standard additions requires preparing
calibration standards in the sample matrix rather than reagent water or
blank solution. It requires taking four identical aliquots of the
solution and adding known amounts of standard to three of these aliquots.
The forth aliquot is the unknown. Preferably, the first addition should
be prepared so that the resulting concentration is approximately 50% of
the expected concentration of the sample. The second and third additions
should be prepared so that the concentrations are approximately 100% and
150% of the expected concentration of the sample. All four aliquots are
maintained at the same final volume by adding reagent water or a blank
solution, and may need dilution adjustment to maintain the signals in the
linear range of the instrument technique. All four aliquots are analyzed.
8.4.3 Prepare a plot, or subject data to linear regression, of
instrument signals or external-calibration-derived concentrations as the
dependant variable (y-axis) versus concentrations of the additions of
standard as the independent variable (x-axis). Solve for the intercept of
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the abscissa (the independent variable, x-axis) which is the concentration
in the unknown.
8.4.4 Alternately, subtract the instrumental signal or external -
calibration-derived concentration of the unknown (unspiked) sample from
the instrumental signals or external-calibration-derived concentrations of
the standard additions. Plot or subject to linear regression of the
corrected instrument signals or external-calibration-derived concentra-
tions as the dependant variable versus the independent variable. Derive
concentrations for unknowns using the internal calibration curve as if it
were an external calibration curve.
8.5
periods:
Samples must undergo TCLP extraction within the following time
SAMPLE MAXIMUM HOLDING TIMES [Days]
Volatiles
Semi-volatiles
Mercury
Metals, except
mercury
From:
Field
collection
To:
TCLP
extraction
14
14
28
180
From:
TCLP
extraction
To:
Preparative
extraction
NA
7
NA
NA
From:
Preparative
extraction
To:
Determinative
analysis
14
40
28
180
Total
elapsed
time
28
61
56
360
NA = Not applicable
If sample holding times are exceeded, the values obtained will be considered
minimal concentrations. Exceeding the holding time is not acceptable in
establishing that a waste does not exceed the regulatory .level. Exceeding the
holding time will not invalidate characterization if the waste exceeds the
regulatory level.
9.0 METHOD PERFORMANCE
9.1 Ruggedness. Two ruggedness studies have been performed to determine
the effect of various perturbations on specific elements of the TCLP protocol.
Ruggedness testing determines the sensitivity of small procedural variations
which might be expected to occur during routine laboratory application.
9.1.1 Metals - The following conditions were used when leaching
a waste for metals analysis:
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Varying Conditions
Liquid/Solid ratio
Extraction time
Headspace
Buffer #2 acidity
Acid-washed filters
Filter type
Bottle type
19:1 vs. 21:1
16 hours vs. 18 hours
20% vs. 60%
190 meq vs. 210 meq
yes vs. no
0.7 jim glass fiber vs.
vs. polycarbonate
borosilicate vs. flint
0.45 im
glass
Of the seven method variations examined, acidity of the extraction
fluid had the greatest impact on the results. Four of 13 metals from an
API separator sludge/electroplating waste (API/EW) mixture and two of
three metals from an ammonia lime still bottom waste were extracted at
higher levels by the more acidic buffer. Because of the sensitivity to pH
changes, the method requires that the extraction fluids be prepared so
that the final pH is within + 0.05 units as specified.
9.1.2 Volatile Organic Compounds - The following conditions were
used when leaching a waste for VOC analysis:
Varying Conditions
Liquid/Solid ratio
Headspace
Buffer #1 acidity
Method of storing extract
Aliquotting
Pressure behind piston
19:1 vs. 21:1
0% vs. 5%
60 meq vs. 80 meq
Syringe vs. Tedlar*
bag
yes vs. no
0 psi vs. 20 psi
None of the parameters had a significant effect on the results of
the ruggedness test.
9.2 Precision. Many TCLP precision (reproducibility) studies have been
performed, and have shown that, in general, the precision of the TCLP is
comparable to or exceeds that of the EP toxicity test and that method precision
is adequate. One of the more significant contributions to poor precision appears
to be related to sample homogeneity and inter-laboratory variation (due to the
nature of waste materials).
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9.2.1 Metals - The results of a multi-laboratory study are shown
in Table 6, and indicate that a single analysis of a waste may not be
adequate for waste characterization and identification requirements.
9.2.2 Semi-Volatile Organic Compounds - The results of two
studies are shown in Tables 7 and 8. Single laboratory precision was
excellent with greater than 90* percent of the results exhibiting an RSD
less than 25 percent. Over 85 percent of all individual compounds in the
multi-laboratory study fell in the RSD range of 20 - 120 percent. Both
studies concluded that the TCLP provides adequate precision. It was also
determined that the high acetate content of the extraction fluid did not
present problems (i.e., column degradation of the gas chromatograph) for
the analytical conditions used.
9.2.3 Volatile Organic Compounds - Eleven laboratories
participated in a collaborative study of the use of the ZHE with two waste
types which were fortified with a mixture of VOCs. The results of the
collaborative study are shown in Table 9. Precision results for VOCs tend
to occur over a considerable range. However, the range and mean RSD
compared very closely to the same collaborative study metals results in
Table 6. Blackburn and Show concluded that at the 95% level of signifi-
cance: 1) recoveries among laboratories were statistically similar, 2)
recoveries did not vary significantly between the two sample types, and 3)
each laboratory showed the same pattern of recovery for each of the two
samples.
10.0 REFERENCES
1. Blackburn, W.B. and Show, I. "Collaborative Study of the Toxicity
Characteristics Leaching Procedure (TCLP)." Draft Final Report, Contract No. 68-
03-1958, S-Cubed, November 1986.
2. Newcomer, L.R., Blackburn, W.B., Kimmell, T.A. "Performance of the
Toxicity Characteristic Leaching Procedure." Wilson Laboratories, S-Cubed, U.S.
EPA, December 1986.
3. Williams, L.R., Francis, C.W.; Maskarinec, M.P., Taylor D.R., and Rothman,
N. "Single-Laboratory Evaluation of Mobility Procedure for Solid Waste." EMSL,
ORNL, S-Cubed, ENSECO.
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Table 1.
Volatile Analytes1-2
Compound ' CAS No.
Acetone
Benzene
n-Butyl alcohol
Carbon disulfide
Carbon tetrachloride
Chlorobenzene
Chloroform
1,2-Dichloroethane
1 , 1 -Di chl oroethyl ene
Ethyl acetate
Ethyl benzene
Ethyl ether
Isobutanol
Methanol
Methyl ene chloride
Methyl ethyl ketone
Methyl isobutyl ketone
Tetrachl oroethylene
Toluene
1,1,1, -Tri chl oroethane
Tri chl oroethyl ene
Trichl orof 1 uoromethane
l,l,2-Trichloro-l,2,2-trifluoroethane
Vinyl chloride
Xylene
67-64-1
71-43-2
71-36-3
75-15-0
56-23-5
108-90-7
67-66-3
107-06-2
75-35-4
141-78-6
100-41-4
60-29-7
78-83-1
67-56-1
75-09-2
78-93-3
108-10-1
127-18-4
108-88-3
71-55-6
79-01-6
75-69-4
76-13-1
75-01-4
1330-20-7
1 When testing for any or all of these analytes, the zero-headspace
extractor vessel shall be used instead of the bottle extractor.
2 Benzene, carbon tetrachloride, chlorobenzene, chloroform,
1,2-dichloroethane, 1,1-dichloroethylene, methyl ethyl ketone,
tetrachloroethylene, and vinyl chloride are toxicity characteristic
constituents.
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Table 2.
Suitable Rotary Agitation Apparatus1
Company
Location
Model No.
Analytical Testing and
Consulting Services,
Inc.
Associated Design and
Manufacturing Company
Warrington, PA
(215) 343-4490
Alexandria, VA
(703) 549-5999
Environmental Machine and
Design, Inc.
IRA Machine Shop and
Laboratory
Lars Lande Manufacturing
Mi Hi pore Corp.
Lynchburg, VA
(804) 845-6424
Santurce, PR
(809) 752-4004
Whitmore Lake, MI
(313) 449-4116
Bedford, MA
(800) 225-3384
4-vessel extractor (DC20S)
8-vessel extractor (DC20)
12-vessel extractor (DC20B)
24-vessel extractor (DC24C)
2-vessel
4-vessel
6-vessel
8-vessel
12-vessel
24-vessel
(3740-2-BRE)
(3740-4-BRE)
(3740-6-BRE)
(3740-8-BRE)
(3740-12-BRE)
(3740-24-BRE)
8-vessel (08-00-00)
4-vessel (04-00-00)
8-vessel (011001)
10-vessel (10VRE)
5-vessel (5VRE)
6-vessel (6VRE)
4-ZHE or
4 2-liter bottle
extractor (YT310RAHW)
1 Any device that rotates the extraction vessel in an end-over-end fashion at 30
i 2 rpm is acceptable.
1311- 25
Revision 0
July 1992
-------
Table 3.
Suitable Zero-Headspace Extractor Vessels1
Company
Location
Model No.
Analytical Testing &
Cpnsulting Services; Inc.
Associated Design and
Manufacturing Company
Lars Lande Manufacturing2
Mi11i pore Corporat i on
Environmental Machine
and Design, Inc.
Gelman Science
Harrington, PA
(215) 343-4490
Alexandria, VA
(703) S49.-5999
Whitmore Lake, MI
(313) 449-4116
Bedford, MA
(800) 225-3384
Lynchburg, VA
(804) 845-6424
Ann Arbor, MI
(800) 521-1520
C102, Mechanical
Pressure Device
3745-ZHE, Gas
Pressure Device
ZHE-11,, Gas
Pressure Device
YT30090HW, Gas
Pressure Device
VOLA-TOX1, Gas
Pressure Device
15400 Gas Pressure
Device
1 Any device that meets, the specifications listed in Section 4.2.1 of the method
is suitable.
2 This device uses a 110 mm filter.
1311- 26
Revision 0
July 1992
-------
Table 4.
Suitable Filter Holders1
Model/
Company
Nucleopore Corporation
Micro Filtration
Systems
Location
.Pleasanton, CA
(800) 882r77:Il
Dublin, CA .
(800) 334-7132
(415) 828-6010
Catalogue No.
425910
410400
302400
311400
Size
142 mm
47 mm
142 mm
47 mm
Millipore Corporation Bedford, MA YT30142HW 142 mm
(800) 225-3384 XX1004700 47 mm
1 Any device capable of separating the liquid from the solid phase of the waste
is suitable, providing that it is chemically compatible with the waste and the
constituents to be analyzed. Plastic devices (not-listed above) may be used when
only inorganic analytes are of concern, The 142 mm size filter holder is
recommended. . ,
1311- 27 Revision 0
July 1992
-------
Table 5.
Suitable Filter Media1
Company
Mi Hi pore Corporation
Nucleopore Corporation
Whatman Laboratory
Products, Inc.
Micro Filtration
Location
Bedford, MA
(800) 225-3384
Pleasanton, CA
(415) 463-2530
Clifton, NJ
(201) 773-5800
Dublin, CA
Model
AP40
211625
6FF
GF75
Pore
Size
(/xm)
0.7
0.7
0.7
0.7
Systems
Gelman Science
(800) 334-7132
(415) 828-6010
Ann Arbor, MI
(800) 521-1520
66256 (90mm)
66257 (142mm)
0.7
1 Any filter that meets the specifications in Section 4.4 of the Method is
suitable.
1311- 28
Revision 0
July 1992
-------
Table 6. Multi-Laboratory TCLP Metals, Precision
Waste
Ammonia
Lime Still
Bottoms
API/EW
Mixture
Fossil
Fuel Fly
Ash
Extraction
Fluid
#1
n
#1
n
#1
n
#1
#2
#1
n
#1 .
#2
#1
n
#1
#2
#1
n
Metal
Cadmium
Chromium
Lead
Cadmium
Chromium
Lead
Cadmium
Chromium
Lead
X
0.053
0.023
0.015
0.0032
0.0030
0.0032
0.0046
0.0005
0.0561
0.105
0.0031
0.0124
0.080
0.093
0.017
0.070
0.0087
0.0457
S
0.031
0.017
0.0014
0.0037
0.0027
0.0028
0.0028
0.0004
0.0227
0.018
0.0031
0.0136
0.069
0.067
0.014
0.040
0.0074
0.0083
%RSD
60
76
93
118
90
87
61
77
40
17
100
110
86
72
85
57
85
18
%RSD Range =17-118
Mean %RSD = 74
NOTE: X = Mean results from 6-12 different laboratories
Units = mg/L
Extraction Fluid #1 = pH 4.9
#2 = pH 2.9
1311- 29
Revision 0
July 1992
-------
Table 7. Single-Laboratory Semi-Volatiles, Precision
Waste
Ammonia
Lime Still
Bottoms
API/EW
Mixture
Compound
Phenol
2-Methyl phenol
4-Methyl phenol
2,4-Dimethylphenol
.
Naphthalene
2-Methyl naphtha! ene
Dibenzofuran
Acenaphthylene
Fluorene
Phenanthrene
Anthracene
Fluoranthrene
Phenol
2,4-Dimethylphenol
Naphthalene
2-Methyl naphtha! ene
Extraction
Fluid
#1
#2
#1
#2
#1
#2
#1
n
n
n
#1
12
#1
#2
#1
n
n
n
#1
n
n
n
n
n
#1
n
n
n
n
n
#1
n
X
19000
19400
2000
1860
7940
7490
321
307
3920
3827
290
273
187
187
703
663
151
156 .
241
243
33.2
34.6
25.3
26.0
40.7
19.0
33.0
43.3
185
165
265
200
S
2230
929
297
52.9
1380
200
46.8
45.8
413
176
44.8
19.3
22.7
7.2
89.2
20.1
17.6
2.1
22.7
7.9
6.19
1.55
1.8
1.8
13.5
1.76
9.35
8.61
29.4
24.8
61.2
18.9
%RSD
11.6
4.8
14.9
2.8
17.4
2.7
14.6
14.9
10.5
4.6
15.5
7.1
12.1
3.9
12.7
3.0
11.7
1.3
9.4
3.3
18.6
4.5
7.1
7.1
33.0
9.3
28.3
19.9
15.8
15.0
23.1
9.5
%RSD Range =1-33
Mean %RSD = 12
NOTE:
Units =
Extractions were performed in triplicate
All results were at least 2x the detection limit
Extraction Fluid n = pH 4.9
#2 = pH 2.9
1311- 30
Revision 0
July 1992
-------
Table 8. Multi-Laboratory Semi-Volatiles, Precision
Waste
Ammonia Lime
Still Bottoms (A)
API/EW
Mixture (B)
Fossil Fuel
Fly Ash (C)
Compound
BNAs
BNAs
BNAs
Extraction
Fluid
#1
#2
#1
#2
#1
#2
X
10043
10376
1624
2074
750
739
S
7680
6552
675
1463
175
342
%RSD
76.5
63.1
41.6
70.5
23.4
46.3
Mean %RSD = 54
NOTE: Units =
X = Mean results from 3-10 labs
Extraction Fluid #1 = pH 4.9
n = pH 2.9
%RSD Range for Individual Compounds
A, #1 0 - 113
A, n 28 - 108
B, #1 20 - 156
B, #2 49 - 128
C, #1 36 - 143
C, #2 61 - 164
1311- 31
Revision 0
July 1992
-------
Table 9. Multi-Laboratory (11 Labs) VOCs, Precision
Waste
Mine
Tailings
Ammonia
Lime Still
Bottoms
Compound
Vinyl chloride
Methyl ene chloride
Carbon disulfide
1,1-Dichloroethene
1,1-Dichloroethane
Chloroform
1,2-Dichloroethane
2-Butanone
1 , 1 , 1 -Tri chl oroethane
Carbon tetrachloride
Trichloroethene
1 , 1 , 2-Tri chl oroethene
Benzene
1,1,2 , 2-Tetrachl oroethane
Toluene
Chlorobenzene
Ethyl benzene
Tri chl orof 1 uoromethane
Acrylonitrile
Vinyl chloride
Methyl ene chloride
Carbon disulfide
1,1-Dichloroethene
1,1-Dichloroethane
Chloroform
1,2-Dichloroethane
2-Butanone
1,1,1-Trichloroethane
Carbon tetrachloride
Trichloroethene
1 , 1 , 2-Tri chl oroethene
Benzene
1,1,2, 2-Tetrachl oroethane
Toluene
Chlorobenzene
Ethyl benzene
Tri chl orof 1 uoromethane
Acrylonitrile
X
6.36
12.1
5.57
21.9
31.4
46.6
47.8
43.5
20.9
12.0
24.7
19.6
37.9
34.9
29.3
35.6
4.27
3.82
76.7
5.00
14.3
3.37
52.1
52.8
64.7
43.1
59.0
53.6
7.10
57.3
6.7
61.3
3.16
69.0
71.8
3.70
4.05
29.4
S
6.36
11.8
2.83
27.7
25.4
29.2
33.6
36.9
20.9
8.2
21.2
10.9
28.7
25.6
11.2
19.3
2.80
4.40
110.8
4.71
13.1
2.07
38.8
25.6
28.4
31.5
39.6
40.9
6.1
34.2
4.7
26.8
2.1
18.5
12.0
2.2
4.8
34.8
%RSD
100
98
51
127
81
63
70
85
100
68
86
56
76
73
38
54
66
115
144
94
92
61
75
49
44
73
67
76
86
60
70
44
66
27
17
58
119
118
%RSD Range = 17 - 144
Mean %RSD = 75
NOTE: Units = /*g/L
1311- 32
Revision 0
July 19*92
-------
Motor
(30± 2 rpm)
J Extraction Vessel Holder
Figure 1. Rotary Agitation Apparatus
Top Flange
Support Screen
Liquid Inlet/Outlet Valve
Support Screen
Vfton o-rings
Bottom Flange—^{_
Pressurized Gas •
intet/CXrttet Valve
.-..-.• .Sample '••'•'• •'-.
Piston
Gas
C_J
Pressure
Gauge
Figure 2. Zero-Headspace Extractor (ZHE)
1311- 33
Revision 0
July 1992
-------
METHOD 1311
TOXICITY CHARACTERISTIC LEACHATE PROCEDURE
/ START j
,,
U*e a
•ub-sanple
•a*te
of
Separate
liquids from
solids «ith 0.6
• 0 8 UB glass
fiber filter
Discard
Separate
liquid* fren
solids »ith 0 6
• 0 8 un glass
'fiber 'filter"
Eitract «/
.appropriate fluid
1) Bottle eitraetor
for- non-volatiles
2) 2HE device, for
•volatile*
Reduce
particle size
to <9.5 mm
1311- 34
Revision 0
July 1992
-------
METHOD 1311 (CONTINUED)
TOXICITY CHARACTERISTIC LEflCHATE PROCEDURE
Discard
solids
Solid
. Separate
eitract from
solids ./ 0.6
0 8 urn glass
fiber filter
Is
liquid
compatible "X. No
•ith the
extract?
Measure amount ef
liquid and analyze
[mathematically
combine result •/
result of extract
analysis)
Combine
extract •/
liquid phase
of vaste
Analyze
liquid
1311-35'
Revision 0
July 1992
-------
CD
Q.
X*'
-------
Appendix IV
USEPA Region II
Organic, Inorganic and TCLP Data Validation
Methods
-------
Evaluation of Hrtals Data for the contract Laboratory
based on
(CLP)
SO?. 3/90
(BOP Revision XI)
i, Quality Assurance Chemist
Toxic and hazardous Waste Section
OKIE: -^ —
APPROVED BY:
APPH0VH) BY
Boberx Runyon,
Monitoring
Branch
DATE:
Kevin Kubik, Chief
Toxic and Hazardous Waste Section
DATE;
-------
STANDARD OPERATING PROCEDURE
Title: Evaluation of Metals Data for the
OcaiLxaot Laboratory Program
Page 1 of 35
Date: Sept. 1991
Number: HW-2
Revision: 11
1.0
1.1 Diis procedure is applicable to inorganic data obtained from contractor
laboratories working for Hazardous Waste Site Contract Laboratory
Program (CLP).
1.2 The. data validation is based upon analytical and quality assurance
requirements specified in Statement of Work (SOW) 3/90.
2.0 Bpqponsi>M T •» ties - Data reviewers will complete the following tasks as assigned by the Data
Review Coordinator:
2.1. For a total
revew:
2.1.1
tics" Checklist Aonendix
The reviewer must answer every question on the checklist.
The answer on the checklist must match the action in the narrative
(appendix A.2) and on Form I's. Do not use pencil to write the narrative.
2.1.3 Contract Nuu-Ouuiplianee - SO Report (Appep*i-g * "*)
Ihis report is to be completed only when a serious contract violation is
encountered, or upon the request of the Data Review Manager or Deputy Project
Officer (DPO) . Forward 5 copies: one each for internal files, appropriate
Regional DPO, Sample Management Office (SMD) and last two addresses of
Mailing List for Data Reviewers (Appendix A.4) . In other cases, all contract
violations should be appended to end of Data Assessment Narrative (Sec. A.2. 2)
2.1.4
g""«"-«i'
— gimniar pf Tneyrvm^ c Qu
^
Enter in ink on Data Summary Sheet required QC values from Forms I through IX.
all values that require data qualification "Action".
Circle
2.1.5.1 Appendix A.6
Fill in the total number of analytes analyzed by different analyses and
the number of analytes rejected or flagged as estimated due to corresponding
quality control criteria. Place an "X" in boxes where analyses were not
performed, or criteria do not apply.
1.5.2 Appendix A. 7
Data reviewer is also required to fill out Inorganic Regional Data Assessment
-------
form (Appendix A.7) provided by EPA Headquarters. Codes listed on the form
will be \ipgH to describe the Data Assessment Summary.
STANDARD OPERATING PROCEDURE Page 2 of 35
Title: Evaluation of Metals Data for the Date: Sept. 1991
Contract laboratory Program Number: HW-2
Revision: 11
2.1.6 Data Review Log; It is recommended that each data reviewer should maintain a log of the
reviews completed to include: a. date of start of case review
b. date of completion of case review
c. site
d. case number
e. contract laboratory
f . number of samples
g. matrix
h. hours worked
i. reviewer's initials
2.1.7 Telephone Record Log - the data reviewer should enter the bare facts of
inquiry, before initiating any phone conversation with CLP laboratory.
After the case review has been completed, mail white copy of Telephone
Record Log to the laboratory and pink copy to SMD. File yellow copy in
the Telephone Record log folder, and attach a xerox copy of the Telephone
Record log to the completed Data Assessment Narrative (Appendix A.2) .
2.1.8 foxv^T^f^ Paperwork
2.1.8.1 Upon completion of review, the following are to be forwarded to the Regional
Sample Control Center (RSCC) located in the Surveillance and Monitoring Branch:
a. data package
b. completed data assessment checklist (Appendix A. 1, original)
c. SMD Contract Compliancy Screening (CCS}
d. Data Summary Sheet (Appendix A. 5) along with completed Data Assessment
Narrative (Appendix A.2)
e. Record of Communication (copy)
f . CLP Reanalysis Request/Approval Record (original + 3 copies)
g. Appendix A.7 (original) .
2.1.8.2 Forward 2 copies of completed Data Assessment Narrative (Appendix A.2)
along with 2. copies of the Inorganic Data aesaaggmprrt- Form (Appendix A.7) and
Telephone Record log , if any, : one each for appropriate Regional TPO,
and the other one to EPA EMSL office in Las Vegas. The addresses of TPOs and EPA office
in Las Vegas are given in Appendix A-4.
-------
STANDARD OPERATING PROCEDURE Page 3 of 35
Title: Evaluation of Metals Data for the Date: Sept. 1991
Contract laboratory Program Number: HW-2
Revision: 11
2.1.9 Filed Paperwork - Upon completion of review, the following are to be filed
within MMB files:
a. Two copies of completed Data Assessment Narrative (Appendix A.2) each carrying
Appendix A.7.
b. Telephone Record log (copy)
c. SMD Report (copy Appendix A-3)
d. CLP Reanalysis Request/Approval Record (copy)
Each data package is checked by a Regional Sample Control Coordinator (RSSC) for
completeness. A data package is assumed to be complete when ail the deliverables
required under the contract are present. If a data package is incomplete, the RSSC
would call the laboratory for missing document(s) . If the laboratory does not respond
within a week, SMD and MMB coordinator of Region n will be notified.
4 . .dejection of Data - All values rWwm-inari to be unacceptable on the Inorganic Analysis Data
Sheet (Form I) must be lined over with a red pencil. As soon as any review criteria causes
data to be rejected, that data can be eliminated from any further review or consideration.
5.0 acceptance Criteria - In order that reviews be consistent among reviewers, acceptance
criteria as stated in Appendix A.I (pages 4-25) should be used. Additional guidance can
be found in the National Inorganic Functional Guidelines of October 1, 1989.
6.0 fflP Contract Cocci iarree screening (PCS) - T^-ig is intended to aid reviewer in locating any
problems, both corrected and uncorrected. However, the validation should be carried out
even if CCS is not present. Resubmittals received from laboratory in response to CCS must
be used by the reviewer.
7.0 Request for Reanalysis - Data reviewers must note all items of contract non-compliance
within Data Assessment Narrative. If holding times and sample storage times have not been
exceeded, TPO may request reanalysis if items of non-compliance are critical to data
assessment. Requests are to be made on "CIP Re-Analysis Request/Approval Record".
8.0 Record of Onmnnnication - Provided by the Regional Sample Control Center (RSCC) to
indicate which data packages have been received and are ready to be reviewed.
9. Asundincr off numbers - The data reviewer will follow the standard practice.
-------
STANDARD OPERATING PROCEDURE Page 4 of 35
Title: Evaluation of Metals Data for the Date: Sept. 1991
Contract Laboratory Program Number: HW-2
Appendix A.I: Data Assessment - Contract Revision: 11
Compliance (Total Review)
YES NO N/A~
A.1.1 OouLraet Qecp1''aT>a** screen? T*T Report (CCS) - Present? [ ]
ACTION; if no, contact RSCC.
A.I. 2 Record of Ormmnri cation (from RSCC) - Present?
ACTION; If no, request from RSCC.
A.I. 3 Trip Report - Present and complete?
ACTION; If no, contact RSCC for trip report.
A. 1.4 cample Tra'ffj.c Report — Present?
legible? [ _ ]
ACTION: If no, request from Regional Sample Control
Center (KSCC) .
A.I. 5 Paver Page - Present?
Is cover page properly filled in and signed by the lab
manager or the manager's designee?
ACTION; If no, prepare Telephone Record Log, and
contact laboratory.
Do numbers of samples correspond to numbers on Record
of
Do sample numbers on cover page agree with sample
numbers on:
(a) Traffic Report Sheet?
(b) Form I's?
ACTION; If no for any of the above, contact RSCC for
clarification .
-------
STANDARD OPERATING PROCEDURE
Page 5 of 35
1- -.e: Evaluation of Metals Data for the
Contract laboratory Program
Appendix A.I: Data Assessment - Contract
Compliance (Total Review)
Date: Sept. 1991
Number: HW-2
Revision: 11
A.1.6
A.1.6.l Are all the Form I through Form IX labeled with:
laboratory name?
Case/SAS number?
EPA sample No.?
SDG No.?
Contract No.?
Correct units?
Matrix?
ACTION: If no for any of the above, note under
Contract Prcbleaffion-^G^ljance section
of the "Data Assessment Narrative".
A. 1.6.2 Do any computation/transcription errors exceed 10% of
reported values on Forms I-IX for:
(NOTE: Check all forms against raw data.)
(a) all analytes analyzed by ICP?
(b) all analytes analyzed by GFAA?
(c) all analytes analyzed by AA Flame?
(d) Mercury?
(e) Cyanide?
ACTION; If yes, prepare Telephone log, contact
laboratory for corrected data and
correct errors with red pencil and initial.
Yes No N/A
[ 3
[ ]
[ 3
-------
STANDARD OPERATING PROCEDURE Page 6 of 35
Title: Evaluation of Metals Data for the Date: Sept. 1991
Contract Laboratory Program Number: HW-2
Appendix A.I: Data Assessment - Contract Revision: 11
Compliance (Total Review)
A.1.7 Raw Data
A. 1.7.1 Digestion Log* for flame AA/ICP (Form XLTI) present?
Digestion Log for furnace AA Form XLTI present?
Distillation Log for mercury Form XLTI present?
Distillation Log for cyanides Form Xin present? [ ]
Are pH values (pH<2 for all metals, pH>12 for cyanide)
present? [ ]
*Weights, dilutions and volumes used to obtain values.
Percent solids calculation present for soils/sediments? [ ]
Are preparation dates present on sample preparation
logs/bench sheets? [ ]
A. 1.7.2 Measurement read out record present? ICP [ ]
Flame AA [ ]
Furnace AA [ ]
Mercury [ ]
Cyanides
A.I.7.3 Are all raw data to support all sample analyses and
QC operations present? [ ]
Legible? [ ]
Properly Labeled? [ ]
flCTICM; If no for any of the above questions
in sections A.I.7.1 through A.I.7.3,
write Telephone Record Log and contact
laboratory for •nasaftwilrhala. rfot-a as ftgfr'i'inat'.gri if pH
-------
STANDARD OPERATING PROCEDURE Page 7 of 35
Title: Evaluation of Metals for the Contract Date: Sept. 1991
laboratory Program Number: HW-2
Appendix A.I: Data Assessment - Contract Revision: 11
Compliance (Total Review)
A.I.8 Holding TSmoa - (aqueous and soil samples )
(Examine sample traffic reports and digestion/distillation logs.)
Mercury analysis (28 days) exceeded?
Cyanide distillation (14 days) exceeded?
Other Metals analysis (6 months).... exceeded?
NOTE; Prepare a list of all samples and analytes
for which holding times have been exceeded. Specify
the number of days from date of collection to the date
of preparation (from raw data). Attach to checklist.
ACTION; if yes, reject (red-line) values less than
Instrument Detection Limit (IDL) and flag
as estimated (J) the values above IDL even
though sample (s) was preserved properly.
.8.2 Is pH of aqueous samples for:
Metals Analysis >2
Cyanides Analysis <12
Action: If yes, flag the associated metals and cyanides
k.1.9 ftym T fKKnal Da+a}
Are all Form I's present and complete?
ACTION; if no, prepare telephone record log and contact
laboratory for submittal.
Are correct units (ug/1 for waters and mg/kg for soils)
indicated on Form I's? [ ]
Are soil sample results for each parameter corrected for
percent solids? [ ]
Are EPA sample # s and corresponding laboratory sample
ID # s the same as on the Cover Page, Form I's and
in the raw data? [ ]
Are all "less than IDL" values properly coded with "U"? [ ]
-------
Was a brief physical description of samples given on Form I's? [ ] _
STANDARD OPERATING PROCEDURE Page 8 of 35
Title: Evaluation of Metals Data for the
Contract Laboratory Program
Appendix A.1: Data Assessment - Contract
Compliance (Total Review)
Date: Sept. 1991
Number: HW-2
Revision: 11
Were the correct concentration qualifiers used with
final data?
ACTION: If no for any of the above, prepare Telephone
Record log, and contact laboratory for corrected
data.
Were any samples diluted beyond the requirements of
contract?
If yes, were dilutions noted on Form I's?
ACTION; If no, note under CXantxart-Problem/NorHScrapliance
of the"Data Assessment Narrative".
YES
m N/A
A.I.10.1
Is record of at least 2 point calibration
present for ICP analysis?
Is record of 5 point calibration pr
Hg analysis?
Tt for
ACTION: If no for any of the above, write in the
Contract Problem/Nori-CXapliance section of
the "Data Assessment Narrative".
A.I.10.2 Is record of 4 point calibration present for:
Flame AA?
Furnace AA?
Cyanides?
MOTE: 1. If less than 4 standards are measured in absorbance
mode, then the remaining st.anda.n3s in concentration
mode must be run immediately after calibration and
be within ±10% of true value.
2. For all AA (except Hg) and Cyanide analyses, one
calibration standard is at CRDL level. If not,
write in the Contxact-Problem/Non-Compliance section
-------
of the "Data Assessment Narrative".
STANDARD OPERATING PROCEDURE Page 9 of 35
Title: Evaluation of Metals Data for the Date: Sept. 1991
Contract Laboratory Program Number: HW-2
Appendix A.I: Data Assessment - Contract Revision: 11
Oanpliance (Total Review)
Flag fljagfxrj a"fo?cl (fata as f^gfrimatMri if standards
are not within +10% of true values. Do not flag
the flrvta 'as. p^ii^t*^; in •linear'- range indicated by
good recovery, of standard(s).
A.I. 10.3 Is correlation coefficient* less than 0.995 for:
Mercury Analysis?
Cyanide Analysis?
Atomic Absorption Analysis?
I: If yes. flag the flF1rt'
-------
STANDARD OPERATING PROCEDURE Page 10 of 35
Title: Evaluation of Metals Data for the Date: Sept. 1991
Contract laboratory Program Number: HW-2
Appendix A.I: Data Assessment - Contract Revision: 11
Compliance (Total Review)
YES NON/A
ACTION: Flag as estimated (J) all positive data (not
flagged with a "U") analyzed between a
calibration standard with %R between 75-89%
(65-79% for Hg; 70-84% for CN) or 111-125%
(121-135% for Hg; 116-130% for CN) recovery and
nearest good calibration standard. Qualify results
CRDL) analyzed (CRI)
for each ICP run? [ ]
(Note: CRI for AL,Ba,Ca,Fe,Mg,Na,or K is not required.)
ACTION; If no for any of the above, flag as estimated
all data falling within the affected ranges.
The affected ranges are:
AA Analysis - **True Value + CRDL
ICP Analysis - **True Value + 2CRDL
CN Analysis - **True Value + 0.5 x True Value.
**True value of CRA, CRI or mid-range standard. Substitute IDL for CRDL when IDL > CRDL.
ite the concentration of the missing mid-range standard from the calibration range.
-------
STANDARD OPERATING PROCEDURE Page 11 of 35
1 — ..e: Evaluation of Metals Data for the Date: Sept. 1991
Contract laboratory Program Number; HW-2
Appendix A.I: Data Assessment - Contract Revision: 11
Compliance (Total Review)
NO N/A
A.I. 12. 2 Was CRI analyzed after ICV/ICB and before the final
CCV/OCB, and twice every eight hours of ICP run? [ _ ] _ _
ACTION: If no, write in Contract Problem/Nori-<3cmpliance
Section of the "Data Assessment Narrative".
A. 1.12. 3 circle on each Form TTB all the percent recoveries that
are outside the acceptance windows.
Are CRA and CRI standards within control limits:
Metals 80 - 120%R? [ _ ] _ _
Is mid-range standard within control limits:
Cyanide 80 - 120%R? [ _ ] _ _
ACTION: flag as estimated all sample results within
the affected ranges if the recovery of the
standard is between 50-79%; flag only positive
data if the recovery is between 121-150%; reject
(red line) all data if the recovery is less
than 50%; reject only positive data if the
recovery is greater than 150%. Qualify 50% of
the samples on either side of CRI standard outside
the control limits.
Note; Flag or reject the final results only when sample
raw data are within the affected ranges and the CRDL
standards are outside the acceptance windows.
f^» 1 * 1 j f^o23i TTji doxwisl dud Offn^^ ^mm Qftl^Jjc^ttnon
A..1.13.1 Present and complete? [ ]
For both AA and ICP when both are used for the
same analyte? [ ]
Was an initial calibration blank analyzed? [ ]
Was a continuing calibration blank analyzed after
every 10 samples or every 2 hours (whichever is more
frequent)? [ ]
ACTION: If no, prepare Telephone Record log, contact
laboratory and write in the Contract-Problems/
Nan-Compliance section of the "Data Assessment Narrative".
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STANDARD OPERATING PROCEDURE Page 12 of 35
Title: Evaluation of Metals Data for the Date: Sept. 1991
Contract Laboratory Program Number: HW-2
Appendix A.I: Data Assessment - Contract Revision: 11
Compliance (Total Review}
YESNON/A~
A.I.13.2 Circle on each Form HI all calibration blank values
that are above CRDL (or 2 x IDL when IDL > CRDL).
Are all calibration blanks (when IDKCRDL) less than or
equal to the Contract Required Detection Limits (CRDLs)? [ ]
Are all calibration blanks less than two
Instrument Detection Limit (when IDL>CRDL)?
ACTION: If no for any of the above, flag as estimated
(J) positive sample results when raw sample
value is less than or equal to calibration
blank value analyzed between calibration blank
with value over CRDL (or 2xIDL) and nearest good
calibration blank.
flag five samples on either side of the
calibration blank outside the control limits.
^4 IDEM TTT (PraPaT^tifl|P T¥lafn1c) —
(Mote: The preparation blank for mercury is the same
as the calibration blank. )
A. 1.14.1 Was one prep, blank analyzed for: each 20. samples? [ _ ]
each batch?
each matrix type?
both AA and ICP when both are used for
the same analyte? [ _ ] _ __
ACTION: If no for any of the above, flag as
estimated (J) all the associated positive
data <10 x IDLs for which prep, blank
was not analyzed.
MQIE; If only one blank was analyzed for more
than 20 samples, then first 20 samples analyzed
do not have to be flagged as estimated (J) .
A.I. 14. 2 Is concentration of prep, blank value greater
than the CRDL when IDL is less than or equal to CRDL? _ [ _ ] _
If yes, is the concentration of the sample with
the least concentrated analyte less than 10 times
the prep.blank? _ [ _ ] _
-------
STANDARD OPERATING PROCEDURE Page 13 of 35
T -- e: Evaluation of Metals Data for the Date: Sept. 1991
Contract laboratory Program Number: HW-2
Appendix A.I: Data Assessment - Contract Revision: 11
Compliance (Total Review)
ACTION; If no, reject (red-line) all positive sample
results when sample raw data are less than 10
times the prep, blank value.
.14.4 Is concentration of prep, blank below the negative CRDL?
ACTION; If yes, reject (red-line) all associated sample
results less than lOxCRDL.
A. 1.15 pryrin IV (TCP Ttvfoyrf^ppav^ {"ho^fr
A 15.1 Present and complete?
(NOTE: Not required for furnace AA, flame AA, mercury,
cyanide and Ca, Mg, K and Na.)
Was ICS analyzed at beginning and end of run
(or at least twice every 8 hours)?
ACTION; If no, flag as estimated (J) all the samples for
which AL, Ca, Fe, or Mg is higher than in ICS.
k.1.15.2 Circle ail values on each Form IV that are more
than + 20% of true or established mean value. Are all
Interference Check Sample results inside the control
limits (± 20%)?
If no, is concentration of Al, Ca, Fe, or Mg lower
than the respective concentration in ICS?
ACTION; If no, flag as estimated (J) those positive
results for which ICS recovery is between 121-150%;
flag all sample results as estimated if ICS
recovery falls within 50-79%; reject (red-line)
those sample results for which ICS recovery is less
than 50%; if ICS recovery is above 150%, reject
positive results only (not flagged with a "U").
YES NO N/A
ACTION: If yes, reject (red-line) all associated
data greater than CRDL concentration but
less than ten t"jn»g the prep, blank value.
A. 1.14. 3 Is concentration of prep, blank value (Form m) less
than two times IDL, when HJL is greater than CRDL?
-------
STANDARD OPERATING PROCEDURE Page 14 of 35
Tj._*e: Evaluation of Metals Data for the Date: Sept. 1991
Contract laboratory Program Number; HW-2
Appendix A.I: Data Assessment - Contract Revision: 11
Compliance (Total Review)
YES TO N/A
A. 1.16 farm V J^ (SDJJCfid S^^le BPCif*7!M'y *• fUi
( Mote: Not required for Ca, Mg, K, and Na (both matrices) , Al, and Fe
(soil only.)
A. 1.16.1 Present and complete for: each 20 samples?
each matrix type? [ ]
each cone, range (i.e. low, mad., high)? [ ]
For both AA and 1CP when both are used for the
same analyte? [ ]
ACTION; If no for any of the above, flag as
estimated (J) all the positive data less
than four times the spiking levels specified
in SOW for which spiked sample was not analyzed.
MOTE; If one spiked sample was analyzed for more
than 20 samples, then first 20 samples
analyzed do not have to be flagged as
tagt-iiret-iafj (J) .
A. 1.16.2 Was field blank used for spiked sample?
ACTION; If yes, flag all positive data less than
4 x spike added as estimated (J) for which
field blank was used as spiked sample.
A.I.16.3 Circle on each Form VA all spike recoveries that
are outside control limits (75% to 125%).
Are all recoveries within control limits?
If no, is sample concentration greater than or equal
to four times spike concentration? [ ]
ACTION; If yes, disregard spike recoveries for analytes
whose concentrations are greater than or equal
to four t-impg spike added. If no, circle those
analytes on Form V for which sample conoentration
is less than four times the spike concentration.
-------
STANDARD OPERATING PROCEDURE Page 15 of 35
Title: Evaluation of Metals Data for the Date: Sept. 1991
Contract laboratory Program Number: HW-2
Appendix A.I: Data Assessment - Contract Revision: 11
Compliance (Total Review)
^" ~~'^ES iroN/A"
Are results outside the.control limits (75-125%)
flagged with "N11 on form I1 sand iRarn VA? [ ]
ACTION: if no, write in the Contract - Problem/Nan -
Compliance section of'"Data Assessment Narrative11.
A..1.16.4
Are any spike recoveries:
(a) less than 30%?
(b) between 30-74%?
(c) between 126-150%?
(d) greater than 150%? [ ]
ACTION; if less than 30%, reject all associated aqueous
data; if between 30-74%, flag all associated
aqueous data as estimated (J) ; if between
126-150%, flag as estimated (J)
aqueous data' not flagged with a "D"; if
greater than 150%, reject (red-line) all
associated aqueous data not flagged with a "U"
\.1.16.5
Are any spite recoveries:
(a) less than 10%?
(b) between 10-74%?
(c) between 126-200%?
(d) greater than 200%?
ACTION: If less than 10%, reject all associated data; if
between 10-74%, flag all associated data as
if between 126-200%; flag as estimated all associated
data was not flagged with a-
-------
STANDARD OPERATING PROCEDURE Page 16 of 35
Title: Evaluation of Metals Data for the Date: Sept. 1991
Contract laboratory Program Number: HW-2
Appendix A.I: Data Assessment - Contract Revision: 11
Compliance (Total Review)
YES 1» N/A
A. 1.17 Form vi (Lab Duplicates)
A.I. 17.1 Present and complete for: each 20 samples? [ _ ] _ _
each matrix type? [ _ ] _ _
each concentration range (i.e. low, med. , high)? [ _ ] _ _
both AA and ICP when both are used for the same
analyte? [ _ ] _ _
If no for any the above, flag as estimated
(j) all the data >CRDL* for which duplicate
sample was not analyzed.
Note; 1. If one duplicate sample was analyzed for
more than 20 samples, then first 20 samples do not
have to be flagged as estimated.
2. If percent solids for soil sample and its duplicate
differ by more than 1%, prepare a Form VI for each
duplicate pair, report concentrations in ug/L
on wet weight basis and calculate RPD or Difference
for each analyte.
A. 1.17.2 Was field blank used for duplicate analysis?
aCTICM: If yes, flag all data >CRDL* as estimated
(J) for which field blank was used as duplicate.
A.I.17.3 Are all values within control limits (RPD 20% or
difference < ±CRDL)?
If no, are all results outside the control limits
flagged with an * on Form I's and VT? [ ]
MTIOM; If no, write in the Contract - Problems/Non-
Conpliance section of "Data Assessment Narrative".
MOTE: 1. RPD is not calculable for an analyte of the
sample - duplicate pair when both values are
less than IDL.
Substitute IDL for CRDL when IDL > CRDL.
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STANDARD OPERATING PROCEDURE Page 17 of 35
Title: Evaluation of Metals Data for the Date: Sept. 1991
Contract laboratory Program Number: HW-2
Appendix A.I: Data Assessment - Contract Revision: 11
Compliance (Total Review)
VE3 NO N/A
2. If lab duplicate result is re j actable due
to coefficient of correlation of MSA,
analytical spUtoe recovery, or duplicate
injections criteria, do not apply precision
criteria.
A.I. 17. 4 aqueous
Circle on each Form VI all values that are:
RPD > 50%, or
Difference > CRDL*
Is any RPD greater than 50% where sample and duplicate
are both greater than or equal to 5 tinny; *CRDL? _ [ _ ] _
Is any *"fference** between sample and duplicate greater
than *CRDL where sample and/or duplicate is less than
5 times *CRDL? _ [ _ ] _
If yes, flag the associated data as
Circle on each Form VI all values that are:
RPD > 100%, or
Difference > 2 x CRDL*
Is any RPD (where sample and duplicate are both
greater than or equal to 5 times *CRDL) :
> 100%?
Is any **difference between sample and duplicate
(where sample and/or duplicate is less than 5x*CRDL) :
> 2x*CRDL?
* Substitute IDL for CRDL when IDL > CRDL.
** Use absolute values of sample and duplicate to calculate
the difference.
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STANDARD OPERATING PROCEDURE Page 18 of 35
T-^e: Evaluation of Metals Data for the Date: Sept. 1991
Contract laboratory Program Number: HW-2
Appendix A.I: Data Assessment - Contract Revision: 11
Compliance (Total Review)
YES NO N?A
ACTION: if yes, flag the associated data as estimated.
A. 1.18 Field Duplicates
A. 1.18.1 Were field duplicates analyzed? [ _ ] _ _
aCTION; If yes, prepare a Form VI for each aqueous field
duplicate pair. Prepare a Form VI for each soil
duplicate pair, if percent solids for sample and
its duplicate differ by more than 1%; report
concentrations of soils in ug/1 on wet weight
basis and calculate RPDs or Difference for each
analyte.
NOTE: l. Do not calculate RFD when both values are
less than IDL.
2. Flag all associated data only for field
duplicate pair.
A.I. 18. 2 Aqueous
Circle all values on self prepared Form VI for
field duplicates that are:
RPD > 50%, or
Difference > CRDL*
Is any RPD greater than 50% where sample and duplicate
are both greater than or equal to 5 times *CRDL? _ [ _ ] _
Is any **difference between sample and duplicate greater
than *CRDL where sample and/or duplicate is less than
5 t.iTres *CRDL? _ [ _ ] _
If yes, flag the aggnr-jqivar} data as estimated.
* Substitute IDL for CRDL when IDL > CRDL.
** Use absolute values of sample and duplicate to calculate the difference.
-------
STANDARD OPERATING PROCEDURE
Title: Evaluation of Metals Data for the
Contract Laboratory Program
Appendix A.I: Data Assessment - contract
Compliance (Total Review)
Page 19 of 35
Date: Sept. 1991
Number: HW-2
Revision: 11
YES NO
N/A
Circle all values on self prepared Form VI for
field duplicates that are:
RPD >100%, or
Difference > 2 x CRDL*
Is any RPD (where sample and duplicate are both
greater than 5 timpff *CRDL) :
Is any **difference between sample and duplicate
(where sample and/or duplicate is less than 5x *CRDL ) :
>2x *CRDL?
ACTION; If yes, flag the associated data as estimated.
(Note: LCS - not
required for aqueous Bg and cyanide analyses.)
Was one ICS prepared and analyzed for:
every 20 water samples?
every 20 solid samples?
both AA and ICP when both are used for the
analyte?
ACTION: If no for any of the above, prepare Telephone
Record Log and contact laboratory for submittal
of results of LCS. Flag as estimated (J) all
the data for which LCS was not analyzed.
NOTE; If only one LCS was analyzed for more than 20
samples, then first 20 samples close to LCS
do not have to be flagged as estimated.
* Substitute IDL for CRDL when IDL > CRDL.
-------
** Use absolute values of sample and duplicate to calculate the difference.
STANDARD OPERATING PROCEDURE Page 20 of 35
Title: Evaluation of Metals Data for the Date: Sept. 1991
Contract Laboratory Program Number: HW-2
Appendix A.I: Data Assessment - Contract Revision: 11
Compliance (Total Review)
YES NO N/A"
A.I.19.2 aqueous LCS
Circle on each Form VU the LCS percent recoveries
outside control limits (80 - 120%) except for aqueous
Ag and Sb.
Is any LCS recovery: less than 50%? [ ]
between 50% and 79%? [ ]
between 121% and 150%?
greater than 150%? [ ]
ACTION; Lass than 50%, reject (red-line) all data/-
between 50% and 79%, flag all associated data
as estimated (J); between 121% and 150%, flag
all positive (not flagged with a "U") results
as estimated; greater than 150%, reject all
positive results.
A.l.19.3 solid LCS
NOTE: 1. If "Pound" value of LCS is rejectable due to duplicate
injections or analytical spike recovery criteria,
regardless of LCS recovery, flag the associated data
as J^gi-'JTna'ttari (J) .
2. If IDL of an analyte is equal to or greater than
true value of LCS, disregard the "Action" below even
though LCS is out of control limits.
Is LCS "Pound" value higher than the control
limits on Form VU?
ACTION: If yes, qualify all associated positive data
as estimated.
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STANDARD OPERATING PROCEDURE Page 21 of 35
Evaluation of Metals Data for the Date: Sept. 1991
Contract laboratory Program Number: HW-2
Appendix A.I: Data Assessment - Contract Revision: 11
Compliance (Total Review)
_ __ _____
Is LCS "Pound" value lower than the Control
limits on Form VII? _ [ _ ] _
ACTIOM: If yes, qualify gll agsnrH a-t-oH ria-ha as
A.1.20 farm TT (ICP Serial
NOTE; Serial dilution analysis is required only
for initial concentrations equal to or
greater than 10 x HDL.
A. 1.20.1 Was Serial Dilution analysis performed for:
each 20 samples?
each matrix type?
each concentration range (i.e. low, med.)? [ ]
ACTION; if no for any of the above, flag as estimated
all the positive data >. lOxIDLs or > CRDL when
lOxIDL < CRDL for which Serial Dilution Analysis
was not performed.
A. 1.20.2 Was field blank(s) used for Serial Dilution Analysis? [ ]
ACTION: if yes, flag all associated data > 10 x IDL
as estimated (J). If IQxTDL < CRDL, flag all
data >; CRDL.
\. 1.20.3 Are results outside control limit flagged with an "E"
on Form I's and Form IX when initial concentration on
Form IX is <=>qua1 to 50 times IDL or greater. [ ] _
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STANDARD OPERATING PROCEDURE Page 22 of 35
Evaluation of Metals Data for the Date: Sept. 1991
Contract laboratory Program Number: HW-2
Appendix A.I: Data Assessment - Contract Revision: 11
Compliance (Total Review)
YES NO N/A
ACTION; if no, write in the Contract-Problem/Non-
Compliance section of the "Data Assessment
Narrative".
A.I. 20. 4 Circle on each Form IX all percent difference
that are outside control limits for initial
concentrations equal to or greater than 10 x IDLs only.
Are any % difference values:
> 10%?
> 100%? _ [ _ ] _
ACTION; Flag as estimated (J) ail the associated sample
data > lOxIDLs (or > CRDL when lOxIDL > CRDL)
for which percent difference is greater than 10%
but less than 100%. Reject (red-line) an the
associated sample results equal to or greater
than lOxIDLs (or > CRDL when lOxIDL < CRDL) for
which PD is greater than or equal to 100%.
Note: Flag or reject on Form I's only the sample results
whose associated raw data are > lOxIDL (or >. CRDL
when lOxIDIx CRDL)
A. 1.21 jftTTtmf^a ftfvatric Abyy^MoP (AA.) Qff
A.I. 21.1 Are duplicate injections present in furnace raw data
(except during full Method of Standard Addition) for
each sample analyzed by GEAA?
ACTION; If no, reject the data on Form I's for which
duplicate injections were not performed.
A.l.21.2 Do the duplicate injection readings agree within 20%
Relative Standard Deviation (RSD) or Coefficient of
Variation (CV) for concentration greater than CRDL? [ _ ] _ _
Was a dilution analyzed for sample with post digestion
spite recovery less than 40%? [ _ ] _ _
ACTION; If no for any of the above, flag all the
associated dgt"* as
-------
ACTION: If yes for any of the above, flag all
the associated data as estimated (J).
ul.22.4 Was proper guantitation procedure followed correctly
as outlined in the SOW on page E-23?
ACTION; If no, note exception under Contract Problem/
Non-Cnnipliance section of the "Data Assessment
Narrative", and prepare a separate list.
STANDARD OPERATING PROCEDURE Page 23 of 35
Ti_j.e: Evaluation of Metals Data for the Date: Sept. 1991
Contract laboratory Program Number: HW-2
Appendix A.I: Data Assessment - Contract Revision: 11
* Compliance (Total Review)
YES; Ito N/A"
A.I.21.3 Is ^analytical spike recovery less than 10% or
greater than 150% for any result? [ ]
ACTION: If yes, reject (red-line) the affected data if
recovery is <10%; reject data not flagged with
"U" if spike recovery is >150%.
IDEE; Reject or flag the data only when the affected
sample (s) was not subsequently analyzed by Method
of Standard Addition.
* Post digestion spike is not required on the pre-digestion spiked sample.
&..1.22 form vm (Method of S*-am«ifc*fd frVHtion Results)
\.1.22.1 Present? [ ]
If no, is any Form I result rrried with "S" or a "+"? [ ]
ACTION: If yes, write request on Telephone Record log
and contact laboratory for submittal of Form vm.
\.1.22.2 Is coefficient of correlation for MSA less than 0.990 for
any sample?
ACTION; If yes, reject (red-line) affected data.
^.1.22.3 Was *MSA required for any sample but not performed?
Is coefficient of correlation for MSA less than 0.995?
Are MSA calculations outside the linear range of the
calibration curve generated at the beginning of the
analytical run?
-------
OFERftUNG IRXEDDKE Page 24 of
Title: Evaluation of Metal s Data for the Date: sept.
Oontxact Laboratory Program Number: H*
Appendix A.1: Data Assessment - Contract Revision: U
Compliance (Total Review)
YES NO
A. 1.23 Dissolved/Total or marqanic/Total analvtes -
A.l.23.1 Were any analyses performed for dissolved as well as
total analytes on the same sample (s). [ ]
Were any analyses performed for inorganic as well as total
(organic + inorganic) analytes on the same sample(s)? [ ]
* MSA is not required on I£S and prep, blank.
NOTE: 1. If yes, prepare a list comparing differences
between all dissolved (or inorganic) and
total analytes. Compute the differences as
a percent of the total analyte only when
dissolved oonoentration is greater than CRDL
as well as total concentration.
2. Apply the following questions only if in-
organic (or dissolved ) results are (i) above
CRDL, and (ii) greater than total constituents.
3. At least one preparation blank, ICS, and LCS
should be analyzed in each analytical run.
A.I.23.2 Is the concentration of any dissolved (or inorganic)
analyte greater than its total concentration by
more than 10%? [ ]
A.I.23.3 Is the concentration of any dissolved (or inorganic)
analyte greater than its total concentration by
more than 50%? [ ]
aanOM; If more than 10%, flag both dissolved (or
inorganic) and total values as estimated (J);
if more than 50%, reject (red-line) the data
for both values.
A.I.24 Form I (Fif»1<8 RlnnTQ -
A.I.24.1 Circle all field blank values on Data Summary Sheet
that are greater than CRDL, (or 2 x IDL when IDL > CRDL).
Is field blank concentration less than CRDL
(or 2 x IDL when IDL > CRDL) for all parameters
of associated arpyamg and goil samples? [ ]
-------
j'erye ^3 OZ OO
Title: Evaluation of Metals Data for the Date: Sept. 1991
Contract laboratory Program Hunter: HW-2
Appendix A.I: Data Assessment - Contract Revision: 11
Compliance (Total Review)
NO
If no, was field blank value already rejected due to
other QC criteria?
acnx»; If no, reject (except field blank results)
an agsnr!j art-ad positive sample data less
than or equal to five times the field blank
value. Reject on Form I's the soil sample
results that when converted to ug/L on wet
basis are less than or equal to five
the field blank value.
A.I.25 ppi^n X> XX- yrT fPfrrificafc-jpp of Tngtrrmifftit'al PaTamofATS) .
A ' 25.1 Is verification report present for:
Instrument Detection Limits (quarterly) ?
ICP Interelement Correction Factors (annually)?
ICP Linear Ranges (quarterly)?
If no, contact TPO of the lab.
A.l.25.2 Form x (Instrument Detection Limits) - (Note: IDL is not
required for Cyanide.)
A. 1.25.2.1 Are TDLft present for: all the analytes?
all the instruments used? [ ]
For both A& and ICP when both are used for the
analyte?
If no for any of the above, prepare
Telephone Record Log and contact
laboratory.
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STANDARD OPERATING FRXEDURE Page 26 of 35
Title: Evaluation of Metals Data for the Date: Sept. 1991
Contract laboratory Program Number: HW-2
Appendix A.1: Data Assessment - Contract Revision: 11
Compliance (Total Review)
A.I.25.2.2 Is IDL greater than CRDL for any analyte?
If yes, is the concentration on Form I of the sample
analyzes on the instrument whose IDL exceeds CRDL,
greater than 5 x CRDL.
Action : If no, •nag as ggt-jjna'tgd ail values less
than five timps IDL of the instrument whose
Tnr. exceeds CRDL.
A.l.25.3
A.I. 25. 3.1 Was any sample result higher than high linear range
of ICP.
Was any sample result higher than the highest
calibration standard for non-ICP parameters?
If yes for any of the above, was the
sample diluted to obtain the result on Form I?
If no, flag the result reported on Form I
as
A. 1.26 Percent Solids of
A.I.26.1 Is soil content in sediment(s) less than 50%?
ACTION: If yes, qualify as estimated all data
not previously rejected or flagged due
to other QC criteria.
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STANDARD OPERATING PROCEDURE Page 27 of 35
Title: Evaluation of Metals Data for the Date: Sept. 1991
Contract laboratory Program Number: HW-2
Appendix A.2: Data Assessment Narrative Revision: 11
Case*
SDGf
contractor
Site
lab
Reviewer
Matrix: Soil
Water
Other
A.2.1 The case description and exceptions, if any, are noted below with reason(s)
for rejection or qualification as eg^-jTnat-^ri value (s) J.
-------
STANDARD OPERATING PROCEDURE Page 28 of 35
Evaluation of Metals Data for the Date: Sept. 1991
Contract laboratory Program Number: HW-2
Appendix A.2: Data Assessment Narrative Revision: 11
&.2.1 (continuation)
-------
STANDARD OPERATING PROCEDURE Page 29 of 35
1 ..e: Evaluation of Metals Data for the Date: Sept. 1991
Contract laboratory Program Number: HW-2
Appendix A.2: Data Assessment Narrative Revision: 11
A. 2.1 (continuation)
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STANDARD OPERATING PROCEDURE Page 30 of 35
Ij._.e: Evaluation of Metals Data for the Date: Sept. 1991
Contract Laboratory Program Number: HW-2
Appendix A. 2: Data Assessment Narrative Revision: 11
k.2.2 Ccntxact-PrcbleiivTtonHDoBmpliance
MMB Reviewer: Date:_
Signature
Sontractcr Reviewer: Date:_
Signature
Verified by: Date:_
STANDARD OPERATING PROCEDURE Rage 31 of 35
_.i.tle: Evaluation of Metals Data for the Date: Sept. 1991
-------
Contract laboratory Program Number: HW-2
Appendix A. 3: Contract Non-Complianoe Revision: 11
(SMD Report)
CCNIRACT NCN-CCMPILIANCE
(SMD REPORT)
Regional Review of Uncontrolled Hazardous Waste
Site Contract laboratory Data Package
CASE NO.
The hardcopied (laboratory name)
Inorganic data package received at Region II has been reviewed and the quality assurance and
performance data sunmut |7«arf. The data reviewed included:
SMD Sample NO.:
Cone. & Matrix:
Contract No. WA87-K025.K026.K027 (SOW787) requires that specific analytical work be done and
that associated reports be provided by the contractor to the Regions, EMSL-LV, and SMD. The
general criteria used to determine the performance were based on an examination of:
- Data Completeness - Duplicate Analysis Results
- Matrix Spike Results - Blank Analysis Results
- Calibration Standards Results - MSA Results
T* -i of non-compliance with the above contract are described below.
Comments:
Reviewer's Initial Date
-------
STANDARD OPERATING PROCEDURE Page 32 of 35
Evaluation of Metals Data for the Date: Sept. 1991
Contract laboratory Program Number: HWr2
' A-4; 'MJailitig T.isfi for steta Rgvieajgrs Revision: 11
-------
STANDARD OPERATING PROCEDURE Page 33 of 35
Title: Evaluation of Metals Data for the Date: Sept. 1991
Contract Laboratory Program Number: H»-2
Appendix A.5: Summary of Inorganics Revision: 11
Quality Control Data
-------
STANDARD OPERATING PROCEDURE Page 34 of 35
Evaluation of Metals Data for the Date: Sept. 1991
Contract laboratory Program Number: Wti-2
Appendix A.6: CIP Data Assessment Revision: 11
Summary Form (Inorganics)
-------
STANDARD OPERATING PROCEDURE Page 35 of 35
Title: Evaluation of Metals Data for the Date: Sept. 1991
Contract laboratory Program Number: HW-2
Appendix A.7: CLP Data Assessment Checklist Revision: 11
Inorganic Analysis
INORGANIC REGIONAL DATA ASSESSMENT Region
CASE NO. SITE
NO. OF SAMPLES/
lABORATORY MATRIX
SDG# . REVIEWER (IF NOT ESD)_
SOW# REVIEWER'S NAME
DPO: ACTION FYI CCMPLEITON DATE
DATA ASSESSMENT SUMMARY
ICP AA Hg CYANIDE
1. HOLDING TIMES
2. CALIBRATIONS
3. BIANK3
4. ICS
5. LCS
S DUPLICATE ANALYSIS
MATRIX SPIKE
8. MSA
9. SERIAL DILOTION
10. SAMPLE VERIFICATION
11. OTHER QC
12. OVERALL ASSESSMENT
O = Data has no problems/or qualified due to minor problems.
M = Data qualified due to major problems.
Z = Data-unacceptable.
X = Problems, but do not affect data.
ACTION ITEMS:
AREAS OF CONCERN:
NOTABLE PERFORMANCE:
-------
SOP NO. HW-6
Revision 18
CLP ORGANICS DATA REVIEW
AND PRELIMINARY REVIEW
BY:
t?
rL4
rue,
Leon Lazarus, Environmental Scientist
Toxi3 and Hazardous Waste Section
BY:
George J^rras, Chemist y
* ^
Toxic and* Hazardous Waste Section
BY: ^- < _ Date
Stelios Gerazounls/ Chemist
Toxic and Hazarddus Waste Section
CONCURRED BY: ^A O . ^ _ Date:
Kevin " Kubptr— C^ief
ma Hazardous Waste Section
APPROVED BY: V^flgf/x/K ~'»gS'6fr* Date: /
Robfert RunyonY Chief /
Monitoring Management Branch
-------
STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
YES NO N/A
PACKAGE COMPLETENESS AND DELIVERABLES
CASE NUMBER: LAB:.
SITE:
1.0 Data Completeness and Deliverables
1.1 Have any missing deliverables been received
and added to the data package? [ 1
ACTION: Call lab for explanation/resubmittal of any
missing deliverables. If lab cannot provide
them, note the effect on review of the
package under the "Contract
Problems/Non-Compliance" section of reviewer
narrative.
1.2 Was SMO CCS checklist included with package? f 1
2.0 Cover Letter SPG Narrative
2.1 Is the Narrative or Cover Letter Present? r 1
2.2 Are Case Number and/or SAS number contained
in the Narrative or Cover letter? f ]
3.0 Data Validation Checklist
The following checklist is divided into three parts.
Part A is filled out if the data package contains any
VOA analyses, Part B for any SNA analyses and Part C
for Pesticide/PCBs.
Does this package contain:
VOA Data?
BNA Data?
Pesticide/PCB data?
Action: Complete corresponding parts of checklist.
- 1 -
-------
STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
YES NO N/A
PART A: VOA ANALYSES
1.0 Traffic Reports and Laboratory Narrative
1.1 Are the Traffic Report Forms present for [ ]
all samples?
ACTION: If no, contact lab for replacement
of missing or illegible copies.
1.2 Do the Traffic Reports or Lab Narrative -
indicate any problems with sample receipt,
condition of samples, analytical problems
or special circumstances affecting the
quality of the data? r 1
ACTION: If any sample analyzed as a soil,
other than TCLP, contains 50%-90%
water, all data should be flagged as
estimated (J). If a soil sample
other than TCLP contains more than
90% water, all data should be
qualified as unusable (R).
ACTION: If samples were not iced upon
receipt at the laboratory, flag all
positive results "J" and all Non-
Detects "UJ".
ACTION: If both VOA vials for a sample have
air bubbles or the VOA vial analyzed
had air bubbles, flag all positive
results "J" and all non-detects "R".
- 2 -
-------
STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
YES NO N/A
2.0 Holding Times
2.1 Have any VOA technical holding times/
determined from date of collection to date of
analysis, been exceeded? [ ]
If unpreserved, aqueous samples maintained at 4°C which are to
be analyzed.for aromatic hydrocarbons must be analyzed within
7 days of collection. If preserved with HC1 (pH<2) and stored
at 4°C, then aqueous samples must be analyzed within 14
days of collection. If uncertain about preservation, contact
sampler to determine whether or not samples were preserved.
The holding time for soils is 10 days.
Table of Holding Time Violations
(See Traffic Report)
Sample Sample Date Date Lab Date
ID Matrix Preserved? Sampled Received Analyzed
ACTION: If technical holding times are exceeded, flag all
positive results as estimated ("J") and sample
quantitation limits as estimated ("UJ"), and document in
the narrative that holding times were exceeded. If
analyses were done more than 14 days beyond holding
time, either on the first analysis or upon re-analysis,
the reviewer must use professional judgement to
determine the reliability of the data and the effects of
additional storage on the sample results. At a minimum,
all results must be qualified "J", but the reviewer may
determine that non-detect data are unusable (R). If
holding times are exceeded by more than 28 days, all non
detect data are unusable (R).
- 3 -
-------
STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
YES NO N/A
3.0 System Monitoring Compound (SMC) Recovery (Form II)
3.1 Are the VOA SMC Recovery Summaries (Form II) present
for each of the following matrices:
a.. Low Water [ ]
b. Low Soil [ J
c. Med Soil r 1
3.2 Are all the VOA samples listed on the appropriate
System Monitoring Compound Recovery Summary for each
of the following matrices:
a. Low Water r ]
b. Low Soil [ ]
c. Med Soil F 1
ACTION: Call lab for explanation/
resubmittals. If missing
deliverables are unavailable,
document effect in data assessments.
3.3 Were outliers marked correctly with an
asterisk? [ ]
ACTION: Circle all outliers in red.
3.4 Was one or more VOA system monitoring
compound recovery outside of contract
specifications for any sample or method
blank? r 1
If yes, were samples re-analyzed? [ J
Were method blanks re-analyzed? r ]
- 4 -
-------
STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
YES Nb N/A
ACTION: If recoveries are > 10% but 1 or
more compounds fail to meet SOW
specifications:
1. All positive results are qualified
as; 'estimated :(J).-. :
2. Flag all non-detects as estimated
. detection limits ("UJ") where
recovery is less than the lower
acceptance limit;.
3. If SMC recoveries ,;are above allowable
levels, do not qualify non-rdetects.
If any system monitoring compound
recovery is <10,% :
, ^ i ',
1. Flag all positive results as
estimated ("J")*
2.. Flag all non-detects as unusable
("R").
Professional judgement should be used to qualify
data that only nave method blank SMC recoveries out
of specification in both original and re-analyses.
Check the internal standard areas.
3.5 Are there any transcription/calculation
errors between raw data and Form II? [ ]
ACTION: If large errors exist, call lab for
explanatipn/resubmittal, make any
necessary corrections and note
errors in the data assessment.
4.0 Matrix Spikes fForm III)
4.1 Is the Matrix Spike/Matrix Spike Duplicate
Recovery Form (Form III) present? [ j
- 5 -
-------
STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
YES NO N/A
4.2 Were matrix spikes analyzed at the required
frequency for each of the following matrices:
a. Low Water r 1
b. Low Soil [ ]
c.. Med Soil r 1
ACTION: If any matrix spike data are missing, take
the action specified in 3.2 above.
4.3 How many VGA spike recoveries are outside QC
limits?
Water Soils
out of 10 out of 10
4.4 How many RPD's for matrix spike and matrix spike
duplicate recoveries are outside QC limits?
Water Soils
out of 5 out of 5
ACTION: No action is taken based on MS/USD
data alone. However, using informed
professional judgement, the MS/MSD
results may be used in conjunction
with other QC criteria to determine
the need for qualification of the
data.
5.0 Blanks (Form IV)
5.1 Is the Method Blank Summary (Form IV)
present? _[ 1
5.2 Frequency of Analysis: for the analysis
of VOA TCL compounds, has a reagent/method
blank been analyzed for each SDG or every
20 samples of similar matrix (low water,
low soil, medium soil), whichever is more
frequent?
- 6 -
-------
STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
YES NO N/A
5.3 Has a VOA method/instrument blank been
analyzed at least once every twelve hours for
each concentration level and GC/MS system
used? r 1
ACTION: If any method blank data are missing, call
lab for explanation/ resubmittal. If
method blank data are not available,
reject (R) all associated positive data.
However, using professional judgement, the
data reviewer may substitute field blank
or trip blank data for missing method
blank data.
5.4 Chromatography: review the blank raw data -
chromatograms (RICs), quant reports or data system
printouts and spectra.
Is the chromatographic performance (baseline
stability) for each instrument acceptable
for VOAs? r 1
ACTION: Use professional judgement to
determine the effect on the data.
6.0
NOTE:
6.1
Contamination
"Water blanks", "drill blanks", and distilled water
blanks" are validated like any other sample, and are
not used to qualify data. Do not confuse them with
the other QC blanks discussed below.
Do any method/instrument/reagent blanks have
positive results (TCL and/or TIC) for VOAs?
When applied as described below, the
contaminant concentration in these blanks are
multiplied by the sample dilution factor and
corrected for % moisture when necessary.
.La
6.2
ACTION:
Do any field/trip/rinse blanks have positive
VOA results (TCL and/or TIC)?
Prepare a list of the samples associated with
each of the contaminated blanks. (Attach a
separate sheet.)
- 7 -
-------
STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
YES NO N/A
NOTE: All field blank results associated to a particular
group of samples (may exceed one per case) must be
used to qualify data. Trip blanks are used to
qualify only those samples with which they were
shipped and are not required for non-aqueous
matrices. Blanks may not be qualified because of
contamination in another blank. Field Blanks & Trip
Blanks must be qualified for system monitoring
compound, instrument performance criteria, spectral
or calibration QC problems.
ACTION: Follow the directions in the table below to qualify
TCL results due to contamination. Use the largest
value from all the associated blanks. If any blanks
are grossly contaminated, all associated data should
be qualified as unusable (R).
Sample cone > CRQL
but < lOx blank
value
Sample cone < CRQL
& <10x blank value
Sample cone > CRQL
& >10x blank value
Methylene
Chloride Flag sample result
Acetone with a "U;
Toluene
2-Butanone
Report CRQL &
qualify "U"
No qualification
is needed
Sample cone > CRQL Sample cone < CRQL & Sample cone > CRQL
but < 5x blank is < 5x blank value value & > 5x blank
value
Other
Contam-
inants
Flag sample result
with a "U"
Report CRQL &
qualify MU"
No qualification
is needed
NOTE: Analytes qualified "U" for blank contamination are
still considered as "hits" when qualifying for
calibration criteria.
- 8 -
-------
STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
YES NO N/A
ACTION: For TIC compounds, if the concentration in the
sample is less than five times the concentration in
the most, contaminated associated blank, flag the
sample data "R" (unusable) .
6.3 Are there field/rinse/equipment blanks
associated with every sample? r 1
ACTION: For low level samples, note in data assessment that
there is no associated field/rinse/equipment blank.
Exception; samples taken from a drinking water tap
do not have associated field blanks.
GG/MS Instrument Performance Check /Form V)
7.0
7.1
7.2
7.3
Are the GC/MS Instrument Performance Check
Forms (Form V) present for Bromofluorobenzene
(BFB)?
Are the enhanced bar graph spectrum and
mass/charge (m/z) listing for the BFB
provided for each twelve hour shift?
-L-l.
Has an instrument performance compound been
analyzed for every twelve hours of sample
analysis per instrument? r ]
- 9 -
-------
STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
YES NO N/A
ACTION: List date, time, instrument ID, and
sample analysis for which no
associated GC/MS tuning data are
available.
DATE TIME INSTRUMENT SAMPLE NUMBERS
ACTION: If lab cannot provide missing data, reject ("R") all
data generated outside an acceptable twelve hour
calibration interval.
7.4 Have the ion abundances been normalized to
m/z 95? r 1
ACTION: If mass assignment is in error,
qualify all associated data as
unusable (R).
7.5 Have the ion abundance criteria been met for
each instrument used? [ 1
ACTION: List all data which do not meet ion
abundance criteria (attach a
separate sheet).
ACTION: If ion abundance criteria are not
met, the Region II TPO must
be notified.
7.6 Are there any transcription/calculation errors
between mass lists and Form Vs? (Check at least
two values but if errors are found, check
more.) J 1
- 10 -
-------
STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
YES NO N/A
7.7 Have the appropriate number of significant
figures (two) been reported? [ 1
ACTION: If large errors exist, call lab for
explanation/resubmittal, make
necessary corrections and document
effect in data assessments.
7.8 Are the spectra of the mass calibration
compound acceptable? _[ 1
ACTION: Use professional judgement to
determine whether associated data
should be accepted, qualified, or
rej ected.
8.0 Target Compound List (TCP Analvtes
8.1 Are the Organic Analysis Data Sheets (Form I VOA)
present with required header information on each
page, for each of the following:
a. Samples and/or fractions as appropriate J 1
b. Matrix spikes and matrix spike
duplicates _[ 1
c. Blanks r 1
8.2 Are the VOA Reconstructed Ion Chromatograms, the
mass spectra for the identified compounds, and the
data system printouts (Quant Reports) included in
the sample package for each of the following?
a. Samples and/or fractions as appropriate [ 1
b. Matrix spikes and matrix spike
duplicates (Mass spectra not required) _[ 1
c. Blanks [ 1
ACTION: If any data are missing, take action
specified in 3.2 above.
- 11 -
-------
STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
YES NO N/A
8.3 Are the response factors shown in the Quant
Report? r 1
8.4 Is chromatographic performance acceptable with
respect to:
Baseline stability? r 1
Resolution? _[ 1
Peak shape? I 1
Full-scale graph (attenuation)? [ 1
Other: '
ACTION: Use professional judgement to
determine the acceptability of the
data.
8.5 Are the lab-generated standard mass spectra
of the identified VOA compounds present for
each sample? r 1
ACTION: If any mass spectra are missing,
take action specified in 3.2 above.
If lab does not generate their own
standard spectra, make note in
"Contract Problems/Non-compliance11.
8.6 Is the RRT of each reported compound within
0.06 RRT units of the standard RRT in the
continuing calibration?
8.7 Are all ions present in the standard mass
spectrum at a relative intensity greater
than 10% also present in the sample mass
spectrum?
- 12 -
-------
STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
YES NO JJ7A
8.8 Do sample and standard relative ion
intensities agree within 20%? [ ]
ACTION: Use professional judgement to
determine acceptability of data. If
it is determined that incorrect
identifications were made, all such
data should be rejected (R), flagged
"N" (presumptive evidence of the
presence of the compound) or changed
to not detected (U) at the
calculated detection limit. In
order to be positively identified,
the data must comply with the
criteria listed in 8.6, 8.7, and 8.8.
ACTION: When sample carry-over is a
possibility, professional judgement
should be used to determine if
instrument cross-contamination has
affected any positive compound
identi fication.
9.0 Tentatively Identified Compounds (TIC)
9.1 Are all Tentatively Identified Compound Forms
(Form I Part B) present; and do listed TICs
include scan number or retention time,
estimated concentration and "JN11 qualifier? [ 1
9.2 Are the mass spectra for the tentatively identified
compounds and associated "best match" spectra
included in the sample package for each of the
following:
a. Samples and/or fractions as appropriate .[ 1
b. Blanks I_J.
ACTION: If any TIC data are missing, take
action specified in 3.2 above.
ACTION: Add "JN" qualifier if missing.
- 13 -
-------
STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
YES NO N/A
9.3 Are any TCL compounds (from any fraction)
listed as TIC compounds (example: 1,2-
dimethylbenzene is xylene- a VOA TCL
analyte - and should not be reported as a TIC)? f ]
ACTION: Flag with "R" any TCL compound
listed as a TIC.
9.4 Are all ions present in the reference mass
spectrum with a relative intensity greater
than 10% also present in the sample mass
spectrum? r 1
9.5 Do TIC and "best match" standard relative
ion intensities agree within 20%? [ ]
ACTION: Use professional judgement to
determine acceptability of TIC
identifications. If it is
determined that an incorrect
identification was made, change
identification to "unknown" or to
some less specific identification
(example: "C3 substituted benzene")
as appropriate.
Also, when a compound is not found
in any blank, but is detected in a
sample and is a suspected artifact
of a common laboratory contaminant,
the result should be qualified as
unusable (R). (i.e. Common Lab
Contaminants: C02 (M/E 44) ,
Siloxanes (M/E 73) Hexane, Aldol
Condensation Products, Solvent
Preservatives, and related by
products - see Functional Guidelines
for more guidance) .
- 14 -
-------
STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
YES NO N/A
10.0 Compound Ouantitation and Reported Detection
Limits
10.1 Are there any transcription/calculation
errors in Form I results? Check at least two
positive values. Verify that the correct
internal standard, quantitation ion, and RRF
were used to calculate Form I result. Were
any errors found?
10.2 Are the CRQLs adjusted to reflect sample
dilutions and, for soils, sample moisture? [ ]
ACTION: If errors are large, call lab for
explanation/resubmittal, make any
necessary corrections and note errors
under "Conclusions".
ACTION: When a sample is analyzed at more than one
dilution, the lowest CRQLs are used
(unless a QC exceedance dictates the use
of the higher CRQL data from the diluted
sample analysis). Replace concentrations
that exceed the calibration range in the
original analysis by crossing out the "En
and its associated value on the original
Form I and substituting the data from the
analysis of the diluted sample. Specify
which Form I is to be used, then draw a
red "X" across the entire page of all Form
I's that should not be used, including any
in the summary package.
11.0 Standards Data (GC/MS)
11.1 Are the Reconstructed Ion Chromatograms,
and data system printouts (Quant. Reports)
present for initial and continuing
calibration?
ACTION: If any calibration standard data are
missing, take action specified in
3.2 above.
-L.1
- 15 -
-------
STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
YES NO N/A
12.0 GC/MS Initial Calibration (Form
12.1 Are the Initial Calibration Forms (Form VI)
present and complete for the volatile
fraction at concentrations of 10, 20,
50, 100, 200 ug/1? Are there separate
calibrations for low water/med soils
and low soil samples?
ACTION: If any calibration standard forms are missing, take
action specified in 3.2 above.
12.2 Were all low level soil standards, blanks
and samples analyzed by heated purge? I 1 _
ACTION: If low level soil samples were not heated during
purge, qualify positive hits "J" and non-detects "R"
12.3 Are response factors stable for VOA's
over the concentration range of the
calibration (%Relative Standard Deviation
(%RSD) <30.0% )?
ACTION: Circle all outliers in red.
.L_L
NOTE: Although 11 VOA compounds have a minimum
RRF and no maximum %RSD, the technical
criteria are the same for all analytes.
ACTION: If %RSD > 30.0%, qualify associated positive
results for that analyte "J" and non-detects
using professional judgement. When RSD > 90%,
flag all non-detects for that analyte R (unusable)
NOTE: Analytes previously qualified "U" for blank
contamination are still considered as "hits"
when qualifying for initial calibration
criteria.
12.4 Are the RRFs above 0.05?
Action: Circle all outliers in red.
Action: If any RRF are < 0.05, qualify associated
non-detects (R) and flag associated positive
data as estimated (J).
- 16 -
-------
STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
YESNO N/A
12.5 Are there any transcription/calculation errors
in the reporting of average response factors
(RRF) or %RSD? (Check at least 2 values, but
if errors are found, check more.) .[ ]_
13.0 GC/MS Continuing Calibration (Form VII)
13.1 Are the Continuing Calibration Forms
(Form VII) present and complete for the
volatile fraction? [ 1
13.2 Has a continuing calibration standard
been analyzed for every twelve hours of
sample analysis per instrument? [ ]
ACTION: List below all sample analyses that
were not within twelve hours of the
previous continuing calibration
analysis.
ACTION: If any forms are missing or no continuing
calibration standard has been analyzed within twelve
hours of every sample analysis, call lab for
explanation/resubmittal. If continuing calibration
data are not available, flag all associated sample
data as unusable ("R").
13.3 Do any volatile compounds have a % Difference
(% D) between the initial and continuing
RRF which exceeds the ±25% criteria?
ACTION: Circle all outliers in red.
ACTION: Qualify both positive results and
non-detects for the outlier compound(s)
as estimated. When % D is above 90%, reject
all non-detects for that analyte (R) unusable.
- 17 -
-------
STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
YES NO N/A
13.4 Do any volatile compounds have a RRF <0.05? [ ] _
ACTION: Circle all outliers in red.
ACTION: If the RRF <0.05, qualify associated
non-detects as unusable (R) and "J"
associated positive values.
13.5 Are there any transcription/calculation
errors in the reporting of average response
factors (RRF) or %difference (%D) between
initial and continuing RRFs? (Check at least
two values but if errors are found,
check more.) [ ] .
ACTION: Circle errors in red.
ACTION: If errors are large, call lab for
explanation/resubmittal, make any
necessary corrections and note
errors under "Conclusions".
14.0 Internal Standard fForm VIII)
14.1 Are the internal standard areas (Form VIII)
of every sample and blank within the upper
and lower limits (-50% to + 100%) for each
continuing calibration? £ 1
ACTION: List all the outliers below.
Sample # Internal Std Area Lower Limit Upper Limit
(Attach additional sheets if necessary.)
- 18 -
-------
STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
YES NO N/A
ACTION: 1. If the internal standard area count
is outside the upper or lower limit,
flag with "J" all positive results
quantitated with this internal standard.
2. Non-detects associated with IS area counts
> 100% should not be qualified.
3. If IS area is below the lower limit
(< 50%), qualify all associated non-
detects (U values) "J". If extremely
low area counts are reported, (< 25%)
or if performance exhibits a major
abrupt drop off, flag all associated
non-detects as unusable ("R").
14.2 Are the retention times of the internal
standards within 30 seconds of the
associated calibration standard? r 1
ACTION: Professional judgement should be
used to qualify data if the
retention times differ by more than
3 0 seconds.
15.0 Field Duplicates
15.1 Were any field duplicates submitted for
VOA analysis?
ACTION: Compare the reported results for
field duplicates and calculate
the relative percent difference.
ACTION: Any gross variation between
duplicate results must be addressed
in the reviewer narrative. However,
if large differences exist,
identification of field duplicates
should be confirmed by contacting
the sampler.
- 19 -
-------
STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
YES NO N/A
PART B; SNA ANALYSES
1.0 Traffic Reports and Laboratory Narrative
1.1 Are the Traffic Report Forms present for all
samples? j; 1
ACTION: If no, contact lab for replacement of
missing or illegible copies.
1.2 Do-the Traffic Reports or Lab Narrative
indicate any problems with sample receipt,
condition of samples, analytical problems or
special notations affecting the quality of
the data? r 1
ACTION: If any sample analyzed as a soil, other
than TCLP, contains 50%-90% water,
all data should be flagged as estimated
("J"). If a soil sample, other than TCLP,
contains more than 90% water, all data
should be qualified as unusable (R).
ACTION: If samples were not iced upon receipt at
the laboratory, flag all positive results
11 J" and all non-detects "UJ".
2.0 Holding Times
2.1 Have any BNA technical holding times,
determined from date of collection to date of
extraction, been exceeded? ; [ ]
Continuous extraction of water samples for
BNA analysis must be started within seven
days of the date of collection. Soil/
sediment samples must be extracted within
7 days of collection. Extracts must be
analyzed within 40 days of the date of
extraction.
- 20 -
-------
STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
YES NO N/A
Table of Holding Time Violations
(See Traffic Report)
Sample Date Date Lab Date Date
Sample Matrix Sampled Received Extracted Analyzed
ACTION: If technical holding times are exceeded,
flag all positive results as estimated
("J") and sample quantitation limits
as estimated ("UJ"), and document in
the narrative that holding times were
exceeded.
If analyses were done more than 14 days beyond
holding time, either on the first analysis or
upon reanalysis, the reviewer must use
professional judgement to determine the
reliability of the data and the effects of
additional storage on the sample results.
At a minimum, all results should be qualified
"J", but the reviewer may determine that non-detect
data are unusable ("R"). If holding times are exceeded by
more than 28 days, all non detect data are unusable (R) .
3.0 Surrogate Recovery (Form II)
3.1 Are the BNA Surrogate Recovery Summaries
(Form II) present for each of the following
matrices:
a. Low Water I 1
b. Low Soil J_J_
c. Med Soil r 1
- 21 -
-------
STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
YES NO N/A
3.2 Are all the BNA samples listed on the
appropriate Surrogate Recovery Summaries
for each of the following matrices:
a. Low Water j; _ i
b. Low Soil .[ _ 1
c. Low Soil
ACTION: Call lab for explanation/resubmittals.
If missing deliverables are unavailable,
document effect in data assessments.
3.3 Were outliers marked correctly with an
asterisk? I _ 1
ACTION: Circle all outliers in red.
3.4 Were two or more base-neutral OR acid surrogate
recoveries out of specification for -any sample
or method blank? _[ _ 1
If yes, were samples reanalyzed? .[ _ ].
Were method blanks reanalyzed? _[ _ 1
ACTION: If all BNA surrogate recoveries are
> 10% but two within the base-neutral
or acid fraction do not meet SOW
specifications, for the affected
fraction only fi.e. base-neutral or
acid compounds);
1. Flag all positive results as estimated
("J").
2. Flag all non-detects as estimated
detection limits ("UJ") when recoveries
are less than the lower acceptance limit.
3. If recoveries are greater than the upper
acceptance limit, do not qualify non-detects.
- 22 -
-------
STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
YES NO N/A
If any base-neutral or acid surrogate has a
recovery of <10%:
li Positive results ,for the fraction with
<10% surrogate recovery are qualified
with "J".
2. Non-detects for that fraction should be
qualified as unusable (R) .
Professional judgement should be used to qualify
data that have method blank surrogate recoveries
out of specification in both original and
reanalyses. Check the internal standard areas.
3.5 Are there any transcription/calculation errors
between raw data and Form II? f ]
ACTION: If large errors exist, call lab for
explanation/resubmittal, make any
necessary corrections and document effect
in data assessments.
4.0 Matrix Spikes (Form .1111
4.1 Is the Matrix Spike/Matrix Spike Duplicate
Recovery Form (Form III) present? f 1
4.2 Were matrix spikes analyzed at the required
frequency for each of the following matrices:
a. Low Water
b. Low Soil J[ 1
c. Med Soil r 1
ACTION: If any matrix spike data are missing,
take the action specified in 3.2 above.
- 23 -
-------
STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
YES NO N/A
4.3 How many BNA spike recoveries are outside
QC limits?
Water Soils
out of 22 out of 22
4.4 How many RPD's for matrix spike and matrix
spike duplicate recoveries are outside QC
limits?
Water Soils
out of 11 out of 11
ACTION: No action is taken on MS/MSD data
alone. However, using informed
professional judgement, the data
reviewer may use the matrix spike and
matrix spike duplicate results in
conjunction with other QC criteria and
determine the need for some
qualification of the data.
5.0 Blanks fForm IV)
5.1 Is the Method Blank Summary (Form IV) present? _[ 1
5.2 Frequency of Analysis:
Has a reagent/method blank analysis been
reported per 20 samples of similar matrix,
or concentration level, and for each extraction
batch? r 1
5.3 Has a BNA method blank been analyzed for
each GC/MS system used?
(See SOW p. D - 59/SV, Section 8.7)
ACTION: If any method blank data are missing,
call lab for explanation/resubmittal.
If not available, use professional
judgement to determine if the associated
sample data should be qualified.
- 24 -
-------
STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
YES NO N/A
5.4 Chromatography: review the blank raw data -
chromatograms (RICs), quant reports or data
system printouts and spectra.
Is the chromatographic performance (baseline
stability) for each instrument acceptable for
BNAs? r 1
ACTION: Use professional judgement to determine
the effect on the data.
6.0 Contamination
Note: "Water blanks", "drill blanks" and
"distilled water blanks" are validated
like any other sample and are not used
to qualify the data. Do not confuse them
with the other QC blanks discussed below.
6.1 Do any method/instrument/reagent blanks have
positive results (TCL and/or TIC) for BNAs?
When applied as described below, the
contaminant concentration in these blanks are
multiplied by the sample dilution factor and
corrected for % moisture where necessary. j; ]_
6.2 Do any field/rinse/ blanks have positive
BNA results (TCL and/or TIC)? r 1
ACTION: Prepare a list of the samples associated
with each of the contaminated blanks.
(Attach a separate sheet.)
Note: All field blank results associated to
a particular group of samples (may
exceed one per case) must be used to
qualify data. Blanks may not
be qualified because of contamination
in another blank . Field Blanks must be
qualified for surrogate, spectral, instrument
performance or calibration QC problems.
- 25 -
-------
STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
YES NO N/A
ACTION: Follow the directions in the table
below to qualify TCL results due to
contamination. Use the largest value
from all the associated blanks. If
gross contamination exists, all data
in the associated samples should be qualified
as unusable (R).
Sample cone > CRQL Sample cone CRQL
but < lOx blank is< lOx blank value value & >10x blank
Common Phthalate Esters
Flag sample result Report CRQL & No qualification
with a "U"; qualify "U" is needed
Sample cone > CRQL Sample cone < CRQL & Sample cone > CRQL
but < 5x blank is < 5x blank value value & >5 blank value
Other Contaminants
Flag sample result Report CRQL & No qualification
with a "U"; qualify "U" is needed
NOTE: Analytes qualified "U" for blank contamination
are still considered as "hits" when qualifying
for calibration criteria.
ACTION: For TIC compounds, if the
concentration in the sample is less
than five times the concentration in
the most contaminated associated blank,
flag the sample data "R" (unusable).
6.3 Are there field/rinse/equipment blanks
associated with every sample? [ ")
ACTION: For low level samples, note in data
assessment that there is no associated
field/rinse/equipment blank. Exception:
samples taken from a drinking water tap
do not have associated field blanks.
- 26 -
-------
STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
YES NO N/A
7.0 GC/MS Instrument Performance Check
7.1 Are the GC/MS Instrument Performance Check Forms
(Form V) present for Decafluorotriphenylphosphine
(DFTPP)? F 1
7.2 Are the enhanced bar graph spectrum and mass/
charge (m/z) listing for the DFTPP provided for
each twelve hour shift? r 1
7.3 Has an instrument performance check solution
been analyzed for every twelve hours of sample
analysis per instrument? I 1
ACTION: List date, time, instrument ID, and
sample analyses for which no
associated GC/MS tuning data are
available.
DATE TIME INSTRUMENT SAMPLE NUMBERS
ACTION: If lab cannot provide missing data,
reject ("R") all data generated outside
an acceptable twelve hour calibration
interval.
ACTION: If mass assignment is in error, flag all
associated sample data as unusable (R).
7.4 Have the ion abundances been normalized to m/z
198? F 1
- 27 -
-------
STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
YES NO N/A
7.5 Have the ion abundance criteria been met for
each instrument used?
ACTION: List all data which do not meet ion
abundance criteria (attach a separate
sheet).
ACTION: If ion abundance criteria are not
met, the Region II TPO must
be notified.
7.6 Are there any transcription/calculation errors
between mass lists and Form Vs? (Check at least
two values but if errors are found, check more.) [_J
7.7 Have the appropriate number of significant
figures (two) been reported? J 1
ACTION: If large errors exist, call lab for
explanation/resubmittal, make
necessary corrections and document effect
in data assessments.
7.8 Are the spectra of the mass calibration compound
acceptable? _[ 1
ACTION: Use professional judgement to determine
whether associated data should be
accepted, qualified, or rejected.
8.0 Target Compound List fTCL) Analvtes
8.1 Are the Organic Analysis Data Sheets (Form I SNA)
present with required header information on each
page, for each of the following:
a. Samples and/or fractions as appropriate _[ ]_
b. Matrix spikes and matrix spike duplicates .[ 1
c. Blanks I 1
- 28 -
-------
STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
YES NO N/A
8.2 Has GPC cleanup been performed on all soil/
sediment sample extracts? [ ]
ACTION: If data suggests that GPC was not
performed, use professional judgement.
Make note in !" Contract
Problems/Non-compliance".
8.3 Are the BNA Reconstructed Ion Chromatograms,
the mass, spectra for the iderit if led';^compounds,
and the data jsystem printouts; (Quant Reports)
included in the sample package . for each.of 'the
following?
a. Samples and/or fractions as appropriate r 1
b. Matrix spikes and matrix spike duplicates
(Mass spectra.not required) r 1
c. Blanks r 1
ACTION:/ If any data are missing, take action
specified in 3:i2 'above.
8.4 Are the response factors shown in the Quant
Report? r 1
8.5 Is chromatographie performance acceptable with
respect to:
Baseline stability? r 1
Resolution? [ 1
Peak shape? r 1
Full-scale graph (attenuation)? [ 1
Other: _^ r 1
ACTION: Use professional judgement to determine
the acceptability of the data.*
- 29 -
-------
STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
YESNO N/A
8.6 Are the lab-generated standard mass spectra of
identified SNA compounds present for each
sample? _[ i
ACTION: If any mass spectra are missing, take
action specified in 3.2 above. If lab
does not generate their own standard
spectra, make note in "Contract Problems/
Non-compliance". If spectra are missing,
reject all positive data.
8.7 Is the RRT of each reported compound within 0.06
RRT units of the standard RRT in the continuing
calibration? _[ 1
8.8 Are all ions present in the standard mass
spectrum at a relative intensity greater than
10% also present in the sample mass spectrum? .£ 1
8.9 Do sample and standard relative ion intensities
agree within 20%?
ACTION: Use professional judgement to determine
acceptability of data. If it is
determined that incorrect identifications
were made, all such data should be
rejected (R), flagged "N" (Presumptive
evidence of the presence of the compound)
or changed to not detected (U) at
the calculated detection limit. In order
to be positively identified, the data
must comply with the criteria listed in
8.7, 8.8, and 8.9.
ACTION: When sample carry-over is a possibility,
professional judgement should be used to
determine if instrument cross-contamination
has affected any positive compound
identification.
9.0 Tentatively Identified Compounds (TIC)
9.1 Are all Tentatively Identified Compound Forms
(Form I, Part B) present; and do listed TICs
include scan number or retention time, estimated
concentration and "JN" qualifier? _[ 1
- 30 -
-------
STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
YES NO N/A
9.2 Are the mass spectra for the tentatively
identified compounds and associated "best match"
spectra included in the sample package for each
of the following:
a. Samples and/or fractions as appropriate _[ ]_
b. Blanks r 1
ACTION: If any TIC data are missing, take
action specified in 3.2 above.
ACTION: Add "JN" qualifier if missing.
9.3 Are any TCL compounds (from any fraction) listed
as TIC compounds (example: 1,2-dimethylbenzene is
xylene a VOA TCL - and should not be reported as
a TIC)? r 1
ACTION: Flag with "R" any TCL compound
listed as a TIC.
9.4 Are all ions present in the reference mass
spectrum with a relative intensity greater than
10% also present in the sample mass spectrum? X 1
9.5 Do TIC and "best match" standard relative ion
intensities agree within 20%? r 1
ACTION: Use professional judgement to
determine acceptability of TIC
identifications. If it is determined
that an incorrect identification
was made, change identification to
"unknown" or to some less specific
identification (example: "C3
substituted benzene") as appropriate.
Also, when a compound is not found in
any blank, but is a suspected artifact
of a common laboratory contaminant, the
result should be qualified as unusable
(R).
- 31 -
-------
STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
YES NO N/A
10.0 Compound Ouantitation and Reported Detection Limits
10.1 Are there any transcription/calculation errors in
Form I results? Check at least two positive values.
Verify that the correct internal standard,
guantitation ion, and RRF were used to calculate
Form I result. Were any errors found?
10.2 Are the CRQLs adjusted to reflect sample
dilutions and, for soils, sample moisture? r 1
ACTION: If errors are large, call lab for
explanation/resubmittal, make any
necessary corrections and document
effect in data assessments.
ACTION: When a sample is analyzed at more
than one dilution, the lowest CRQLs
are used (unless a QC exceedance
dictates the use of the higher CRQL
data from the diluted sample analysis).
Replace concentrations that exceed the
calibration range in the original
analysis by crossing out the "E" and it's
associated value on the original Form I
and substituting the data from the analysis
of the diluted sample. Specify which Form I
is to be used, then draw a red " X" across
the entire page of all Form I's that should
not be used, including any in the summary
package.
11.0 Standards Data fGC/MS)
11.1 Are the Reconstructed Ion Chromatograms, and
data system printouts (Quant, Reports) present
for initial and continuing calibration? I 1
ACTION: If any calibration standard data
are missing, take action specified
in 3.2 above.
- 32 -
-------
STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
YES NO N/A
12.0 GC/MS Initial Calibration (Form
12.1 Are the Initial Calibration Forms (Form VI)
present and complete "for the BNA fraction?
ACTION: If any calibration standard forms
are missing, take action specified
in 3.2 above.
12.2 Are response factors stable for BNAs over
the concentration range of the calibration?
(% Relative standard deviation (%RSD) <30.0%) r 1
ACTION: Circle all outliers in red.
NOTE: Although 20 BNA compounds have a minimum
RRF and no maximum %RSD, the technical
criteria are the same for all analytes.
ACTION: If the % RSD is > 30.0%, qualify
positive, results for that analyte "J"
and non-detects using professional
judgement. When RSD > 90%, flag all non-
detect results^ for that analyte R (unusable).
NOTE: Analytes previously qualified "U" due to
blank contamination are still considered
as "hits" when qualifying for calibration
criteria.
12.3 Are all BNA compound RRFs > 0.05? r 1
ACTION: Circle all outliers in red.
ACTION: If any RRF < 0.05
1. "R" all non-detects.
.2. VJ" all positive results.
12.4 Are there any transcription/calculation errors in
the reporting of average response factors (RRF)
or % RSD? (Check at least two values but if errors
are found, check more.) ^ ]
ACTION: Circle Errors in red.
- 33 -
-------
STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
YES NO N/A
ACTION: If errors are large, call lab for
explanation/resubmittal, make any
necessary corrections and note
errors in data assessments.
13.0 GC/MS Continuing Calibration (Form VII)
13.1 Are the Continuing Calibration Forms (Form VII)
present and complete for the BNA fraction? .£ 1
13.2 Has a continuing calibration standard been
analyzed for every twelve hours of sample
analysis per instrument?
ACTION: List below all sample analyses
that were not within twelve hours
of a continuing calibration analysis
for each instrument used.
ACTION: If any forms are missing or no
continuing calibration standard
has been analyzed within twelve
hours of every sample analysis,
call lab for explanation/
resubmittal. If continuing
calibration data are not available,
flag all associated sample data as
unusable ("R").
13.3 Do any send/volatile compounds have a % Difference
(% D) between the initial and continuing RRF
which exceeds the + 25.0% criteria?
ACTION: circle all outliers in red.
ACTION: Qualify both positive results and
non-detects for the outlier
compound(s) as estimated (J) . When %D is
above 90%, reject all non-detects for that
analyte (R) unusable.
- 34 -
-------
STANDARD OPERATING PROCEDURE
Date: January 19912;
Revision: 8
YES NO N/A
f
13.4 Do any semivolatile compounds have a RRF <0.05? f 1 ••'..: -
ACTION: Circle all outliers in red.
ACTION: If RRF <0.05, qualify as unusable (R)
associated non-detects and "J" associated
positive values.
13.5 Are there any transcription/calculation errors
in the reporting of average response factors
(RRF) or % difference (%D)-between initial ^and
continuing RRFs? (Cheek .at least two;-values
but if-errors are found, check more). r ] __
ACTION: Circle errors in red.
ACTION: If errors are large, call lab for
expianation/resiibmittal, make any
necessary corrections and document
effect in data assessments.
14.0 Internal Standards (Form VIII)
14.1 Are the internal standard areas (Form VITI) of ;
every sample -and blank)'within the upper and
lower limits^ (-50% Io *'10.0%) for each continuing
calibration? [ 1
ACTION: List all the outliers below.
Sample # Internal Std Area Lower Limit Upper Limit
(Attach additional sheets if necessary.)
ACTION: 1. If the internal standard area count
is outside the upper or lower limit,
flag With "J" ail positive results
and non-detects (U values) quantitated
with this internal standard.
- 35 -
-------
STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
YES NO N/A
2. Non-detects associated with IS areas
> 100% should not be qualified.
3. If the IS area is below the lower limit
(<50%), qualify all associated non-detects
(U-values) "J". If extremely low area counts
are reported (<25%) or if performance
exhibits a major abrupt drop off, flag all
associated non-detects as unusable (R).
14.2 Are the retention times of the internal standards
within 30 seconds of the associated calibration
standard? [ ]
ACTION: Professional judgement should be
used to qualify data if the
retention times differ by more than
30 seconds.
15.0 Field Duplicates
15.1 Were any field duplicates submitted for BNA
analysis? r 1
ACTION: Compare the reported results for
field duplicates and calculate
the relative percent difference.
ACTION: Any gross variation between field
duplicate results must be addressed
in the reviewer narrative. However,
if large differences exist,
identification of field duplicates
should be confirmed by contacting the
sampler.
- 36 -
-------
STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
YES NO N/A
PART C; PESTICIDE/PCB ANALYSIS
1.0 Traffic Reports and Laboratory Narrative
1.1 Are Traffic Report Forms present for all r 1
samples?
ACTION: If no, contact lab for replacement of
missing or illegible copies.
1.2 Do the Traffic Reports or SDG Narrative indicate
any problems with sample receipt, condition of
the samples, analytical problems or special
circumstances affecting the quality of the data? r 1
ACTION: If any sample analyzed as a soil, other
than TCLP, contains 50%-90% water,
all data should be qualified as estimated
(J) . If a soil sample, other than TCLP,
contains more than 90% water, all data
should be qualified as unusable (R).
ACTION: If samples were not iced upon receipt at
the laboratory, flag all positive results
11 J" and all non-detects »UJ».
2.0 Holding Times
2.1 Have any PEST/PCB technical holding times,
determined from date of collection to date of
extraction, been exceeded? f 1
Water and soil samples for PEST/PCB analysis
must be extracted within 7 days of the date of
collection. Extracts must be analyzed within 40
days of the date extraction.
- 37 -
-------
STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
YES NO N/T
ACTION: If technical holding times are exceeded,
flag all positive results as estimated
(J) and sample quantitation limits (UJ)
and document in the narrative that holding
times were exceeded. If analyses were done
more than 14 days beyond holding time,
either on the first analysis or upon
re-analysis, the reviewer must use
professional judgement to determine the
reliability of the data and the effects
of additional storage on the sample results.
At a minimum, all the data should at least be
qualified "J", but the reviewer may determine
that non-detects are unusable (R) .
3.0 Surrogate Recovery (Form II)
3.1 Are the PEST/PCB Surrogate Recovery Summaries
(Form II) present for each of the following
matrices?
a. Low Water I 1
b. Soil J_J_
3.2 Are all the PEST/PCB samples listed on the
appropriate Surrogate Recovery Summary for
each of the following matrices?
a. Low Water I 1
b. Soil I_l
ACTION: Call lab for explanation/resubmittals.
If missing deliverables are unavailable,
document effect in data assessments.
3.3 Were outliers marked correctly with an
asterisk? I 1
ACTION: Circle all outliers in red.
3.4 Were surrogate recoveries of TCX or DCB
outside of the contract specification for
any sample or blank? (60-150%) [ 1
- 38 -
-------
STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
YES NO N/A
ACTION: No qualification is done if surrogates
are diluted out. If recovery for both
surrogates is below the contract limit,
but above 10%, flag all results for that
sample "J". If recovery is < 10% for
either surrogate, qualify positive
results 'J" and flag non-detects "R".
If recovery is above the contract advisory
limits for both surrogates qualify positive
values "J".
3.5 Were surrogate retention times (RT) within the
windows established during the initial 3-point
analysis of Individual Standard Mixture A? I 1
ACTION: If the RT limits are not met, the
analysis may be qualified unusable (R)
for that sample on the basis of
professional judgement.
3.6 Are there any transcription/calculation errors
between raw data and Form II? [ ]
ACTION: If large errors exist, call lab for
explanation/resubmittal. Make any
necessary corrections and document
effect in data assessments.
4.0 Matrix Spikes (Form III)
4.1 Is the Matrix Spike/Matrix Spike Duplicate
Recovery Form (Form III) present? J 1
4.2 Were matrix spikes analyzed at the required
frequency for each of the following matrices?
(1 MS/MSD must be performed for every 20 samples
of similar matrix or concentration level)
a. Low Water _[ 1
b. Soil r 1
ACTION: If any matrix spike data are missing,
take the action specified in 3.2 above.
- 39 -
-------
STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
YES NO N/A
4.3 How many PEST/PCB spike recoveries are outside
QC limits?
4.4 How many RPD's for matrix spike and matrix spike
duplicate recoveries are outside QC limits?
ACTION: No action is taken on MS/MSD data alone.
However, using informed professional
judgement, the data reviewer may use the
matrix spike and matrix spike duplicate
results in conjunction with other QC
criteria and determine the need for some
qualification of the data.
5.0 Blanks (Form IV)
5.1 Is the Method Blank Summary (Form IV) present?J ].
5.2 Frequency of Analysis: For the analysis of
Pesticide/PCB TCL compounds, has a reagent/
method blank been analyzed for each SDG or
every 20 samples of similar matrix
or concentration or each extraction batch,
whichever is more frequent? [ ]
ACTION: If any blank data are missing, take
the action specified above in 3.2. If
blank data is not available, reject
(R) all associated positive data.
However, using professional judgement,
the data reviewer may substitute field
blank data for missing method blank data.
5.3 Has a PEST/PCB instrument blank been analyzed
at the beginning of every 12 hr. period following
the initial calibration sequence? (minimum
contract requirement)
- 40 -
-------
STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
YE!NO N/A
ACTION: If any blank data are missing, call lab for
explanation/resubmittals. If missing
deliverables are unavailable, document the
effect in data assessments.
5.4 Chromatography: review the blank raw data -
chromatograms, quant reports or data system
printouts.
Is the chromatographic performance (baseline
stability) for each instrument acceptable for
PEST/PCBs? F 1
ACTION: Use professional judgement to determine
the effect on the data.
6.0 Contamination
NOTE: "Water blanks", "distilled water blanks" and
"drilling water blanks" are validated like any
other sample and are not used to qualify the
data. Do not confuse them with the other QC
blanks discussed below.
6.1 Do any method/instrument/reagent/cleanup blanks
have positive results for PEST/PCBs? When applied
as described below, the contaminant concentration
in these blanks are multiplied by the sample
Dilution Factor and corrected for % moisture when
necessary. j; 1
6.2 Do any field/rinse blanks have positive
PEST/PCB results? r 1
ACTION: Prepare a list of the samples associated
with each of the contaminated blanks.
(Attach a separate sheet)
NOTE: All field blank results associated to a particular
group of samples (may exceed one per case or one per
day) may be used to qualify data. Blanks may not be
qualified because of contamination in another blank.
Field blanks must be qualified for
surrogate, or calibration QC problems.
- 41 -
-------
STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
YES NO N/A
ACTION: Follow the directions in the table below
to qualify TCL results due to contamination.
Use the largest value from all the associated blanks.
Sample cone > CRQL Sample cone < CRQL & Sample cone > CRQL
but < 5x blank is < 5x blank value & > 5x blank value
Flag sample result Report CRQL & No qualification
with a "U"; qualify "U" is needed
NOTE: If gross blank contamination exists, all data
in the associated samples should be
qualified as unusable (R).
6.3 Are there field/rinse/equipment blanks associated
with every sample? [ ]
ACTION: For low level samples, note in data assessment
that there is no associated field/rinse/equipment blank.
Exception: samples taken from a drinking water tap
do not have associated field blanks.
7.0 Calibration and GC Performance
7.1 Are the following Gas Chromatograms and Data
Systems Printouts for both columns present
for all samples, blanks, MS/MSD?
a. peak resolution check [ ]
b. performance evaluation mixtures .[ 1
c. aroclor 1016/1260 r 1
d. aroclors 1221, 1232, 1242, 1248, 1254 \ 1
e. toxaphene r 1
f. low points individual mixtures A & B [ ]
g. med points individual mixtures A & B _[ 1
h. high points individual mixtures A & B [ 1
- 42 -
-------
STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
YE! NO
i. instrument blanks £ _ ]_ _
ACTION: If no, take action specified in 3.2 above.
7.2 Are Forms VI - PEST 1-4 present and complete
for each column and each analytical sequence? I _ 1 _
ACTION: If no, take action specified in 3.2
above .
7.3 Are there any transcription/calculation errors
between raw data and Forms VI? _ r 1
ACTION: If large errors exist, call lab for
explanation/resubmittal, make
necessary corrections and
document effect in data assessments.
7.4 Do all standard retention times, including each
pesticide in each level of Individual Mixtures
A & B, fall within the windows established
during the initial calibration analytical
sequence? (For Initial Calibration Standards,
Form VI - .PEST - 1) . r 1 _
ACTION: If no, all samples in the entire
analytical sequence are potentially
affected. Check to see if the
chromatograms contain peaks within an
expanded window surrounding the expected
retention times. If no peaks are found
and the surrogates are visible, non-
detects are valid. If peaks are present
and cannot be identified through pattern
recognition or using a revised RT window,
qualify all positive results and non-detects
as unusable (R) .
For aroclors, RT may be outside the RT window,
but the aroclor may still be identified from the
individual pattern.
7.5 Are the linearity criteria for the initial
analyses of Individual Standards A & B within
limits for both columns? (% RSD must be < 20.0%
for all analytes except for the 2 surrogates,
which must not exceed 30.0 % RSD) . See Form VI
PEST - 2. T 1 _
- 43 -
-------
STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
YESNON/A
ACTION: If no, qualify all associated positive
results generated during the entire
analytical sequence "J" and all non-
detects "UJ". When RSD >90%, flag all
non-detect results for that analyte R
(unusable).
7.6 Is the resolution between any two adjacent
peaks in the Resolution Check Mixture > 60.0%
for both columns? (Form VI-PEST - 4) r 1
ACTION: If no, positive results for compounds
that were not adequately resolved should
be qualified "J". Use professional
judgement to determine if non-detects
which elute in areas affected by co-eluting
peaks should be qualified "N" as presumptive
evidence of presence or unusable (R).
7.7 Is Form VII - Pest-1 present and complete for
each Performance Evaluation Mixture analyzed
during the analytical sequence for both
columns?
ACTION: If no, take action as specified in
3.2 above.
7.8 Has the individual % breakdown exceeded 20.0%
on either column. .[ 1
- for 4,4' - DDT? r 1
- for endrin? r 1
Has the combined % breakdown for 4,4'- DDT/
Endrin exceeded 30.0% on either column?
(required in all instances) _[ ]_
ACTION: 1. If any % breakdown has failed the
QC criteria in either PEM in steps
2 and 17 in the initial calibration
sequence (p. D-38/Pest SOW 3/90),
qualify all sample analyses in the
entire analytical sequence as described
below.
- 44 -
-------
STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
YES NO N/A
2. If any % breakdown has failed the QC
criteria in a PEM Verification
calibration, review data beginning
with the samples which followed the
last in-control standard until the
next acceptable PEM & qualify the
data as described below.
a. 4,4'-DDT Breakdown: If 4,4'-DDT breakdown
is greater than 20.%:
i: Qualify all positive results for DDT
with 'J". If DDT was not detected, but
DDD and DDE are positive, then qualify
the quantitation limit for DDT as
unusable (R) .
ii. Qualify positive results for DDD and/or
DDE as presumptively present at an
approximated quantity (NJ).
b. Endrin Breakdown: If endrin breakdown is greater
than 20.0%:
i. Qualify all positive results for endrin
with "J". If endrin was not detected, but
endrin aldehyde and endrin ketone are
positive, then qualify the quantitation
limit for endrin as unusable (R).
ii. Qualify positive results for endrin ketone and
endrin aldehyde as presumptively present at an
approximated quantity (NJ) .
c. Combined Breakdown: If the combined 4,4'-DDT and
endrin breakdown is greater than 30.0%:
i. Qualify all positive results for DDT and
endrin with "J". If endrin was not
detected, but endrin aldehyde and endrin
ketone are positive, then qualify the
quantitation limit for endrin as unusable
(R). If DDT was not detected, but DDD and
DDE are positive, then qualify the
quantitation limit for DDT as unusable (R).
- 45 -
-------
STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
YES NO N/A
ii. Qualify positive results for endrin ketone
and endrin aldehyde as presumptively present
at an approximated quantity (NJ). Qualify positive
results for DDD and/or DDE as presumptively present
at an approximated quantity (NJ).
7.9 Are the relative percent difference (RPD) values
for all PEM analytes <25.0%? (Form VII-PEST-1) r 1
ACTION: If no, qualify all associated positive
results generated during the analytical
sequence "J" and sample quantitation
limits "UJ".
NOTE: If the failing PEM is part of the
initial calibration, all samples are
potentially affected. If the offending
standard is a verification calibration,
the associated samples are those which
followed the last in-control standard
until the next passing standard.
7.10 Have all samples been injected within a 12 hr.
period beginning with the injection of an
Instrument Blank? [ ]
ACTION: If no, use professional judgement to
determine the severity of the effect
on the data and qualify accordingly.
7.11 Is Form VTI - Pest-2 present and complete for
each INDA and INDB Verification Calibration
analyzed? r 1
ACTION: If no, take action specified in 3.2 above.
7.12 Are there any transcription/calculation errors
between raw data and Form VII - Pest-2? I 1
ACTION: If large errors exists, call lab for
explanation/resubmittal, make any
necessary corrections and document
effect in data assessments.
under "Conclusions".
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STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
YES NO N/A
7.13 Do all standard retention times for each INDA
and INDB Verification Calibration fall within
the windows established by the initial
calibration sequence? r ]
ACTION: If no, beginning with the samples which
followed the last in-control standard,
check to see if the chromatograms contain
peaks within an expanded window surrounding
the expected retention tines. If no peaks
are found and the surrogates are visible,
non-detects are valid. If peaks are present
- and cannot be identified through pattern
recognition or using a revised RT window,
qualify all positive results and non-detects
as unusable (R).
7.14 Are RPD values for all verification calibration
standard compounds < 25.0%? .[ ]_
ACTION: If the RPD is >25.0% for the compound
being quantitated, qualify all associated
positive results "J" and non-detects "UJ".
The "associated samples11 are those which
followed the last in-control standard up
to the next passing standard containing
the analyte which failed the criteria.
If the RPD is >90%, flag all non-detects
for that analyte R (unusable).
8.0 Analytical Sequence Check (Form VIII-PEST)
8.1 Is Form VIII present and complete for each column
and each period of analyses? r 1
ACTION: If no, take action specified in 3.2 above.
8.2 Was the proper analytical sequence followed for
each initial calibration and subsequent analyses?
(see CLP SOW p. D-39 & D-41/PEST) \ 1 .
ACTION: If no, use professional judgement to
determine the severity of the effect
on the data and qualify it accordingly.
Generally, the effect is negligible
unless the sequence was grossly altered
or the calibration was also out of limits.
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STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
YES NO N/A
9.0 Cleanup Efficiency Verification (Form IX)
9.1 Is Form IX - Pest-1 present and complete for each
lot of Florisil Cartridges used? (Florisil Cleanup
is required for all Pest/PCB extracts.) _[ 1
ACTION: If no, take action specified in 3.2 above.
If data suggests that florisil cleanup
was not performed, make note in "Contract
Problems/Non-compliance".
9.2 Are all samples listed on the Pesticide Florisil
Cartridge Check Form? r 1
ACTION: If no, take action specified in 3.2 above.
9.3 If GPC Cleanup was performed, (mandatory for all
soil sample extracts) is Form IX - Pest-2
present? _[ 1
ACTION: If no, take action specified in 3.2 above.
ACTION: If GPC was not performed when required,
make note in" Contract Problems/Non-
Compliance" section of data assessment.
9.4 Are percent recoveries (% R) of the pesticide and
surrogate compounds used to check the efficiency
of the cleanup procedures within QC limits:
80-120% for florisil cartridge check? [ ]
80-110% for GPC calibration? r 1
Qualify only the analyte(s) which fail the recovery
criteria as follows:
ACTION: If % R are < 80%, qualify positive
results "J" and quantitation limits
"UJ". Non-detects should be qualified
"R" if zero %R was obtained for
pesticide compounds. Use professional
judgement to qualify positive results
if recoveries are greater than the upper
limit.
- 48 -
-------
STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
YES NO N/A
NOTE: Sample data should be evaluated for
potential interferences if recovery
of 2,4,5-trichlorophenol was > 5% in the
Florisil Cartridge Performance Check
analysis. Make note in Contract Problems/
Non-Compliance section of reviewer narrative.
NOTE: The raw data of the GPC Calibration
Check analysis is evaluated for pattern
similarity with previously run Aroclor
standards.
10.0 Pesticide/PCB Identification
10.1 Is Form X complete for every sample in which a
pesticide or PCB was detected? .£ 1
ACTION: If no, take action specified in 3.2 above.
10.2 Are there any transcription/calculation errors
between raw data and Forms 6E, 6G, 7E, 7D, 8D, .[ ].
9A, B, 10A.
ACTION: If large errors exist, call lab for
explanation/resubmittal, make necessary
corrections and note error under
"Conclusions".
10.3 Are retention times (RT) of sample compounds
within the established RT windows for both
analyses? .[ 1
Was GC/MS confirmation provided when required
(when compound concentration is > 10 ug/ml in
final extract)? [ 1
Action: Use professional judgement to qualify
positive results which were not confirmed
by GC/MS. Qualify as unusable (R) all
positive results which were not confirmed
by second GC column analysis. Also qualify
as unusable (R) all positive results not
meeting RT window unless associated standard
compounds are similarly biased, (see
Functional Guidelines) The reviewer should
use professional judgement to assign an
appropriate quantitation limit.
- 49 -
-------
STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
YES NO N/A ' "
10.4 Is the percent difference (% D) calculated for the
positive sample results on the two GC columns
< 25.0%? r 1
ACTION: If the reviewer finds neither column
shows interference for the positive
hits, the data should be flagged
as follows:
% Difference Qualifier
25-50 % J
50-90 % JN
> 90 % R
NOTE: The lower of the two values is reported
on Form I. If using professional judgement,
the reviewer determines that the higher
result was more acceptable, the reviewer
should replace the value and indicate the
reason for the change in the data assessment.
10.5 Check chromatograms for false negatives, especially
the multiple peak compounds toxaphene and PCBs.
Were there any false negatives? [ 1 .
ACTION: Use professional judgement to decide
if the compound should be reported. If
the appropriate PCB standards were not
analyzed, qualify the data unusable (R) .
11.0 Compound Quantitation and Reported Detection Limits
11.1 Are there any transcription/calculation errors in
Form I results? Check at least two positive values.
Were any errors found? .£ 1
NOTE: Single-peak pesticide results can be checked for rough
agreement between quantitative results obtained on the two GC
columns. The reviewer should use professional judgement to
decide whethera much larger concentration obtained on one
column versus the other indicates the presence of an
interfering compound. If an interfering compound is
indicated, the lower of the two values should be reported and
qualified as presumptively present at an approximated
quantity (NJ). This necessitates a determination of an
estimated concentration on the confirmation column. The
narrative should indicate that the presence of interferences
has interfered with the evaluation of the second column
confirmation.
- 50 -
-------
STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
YES NO N/A
11.2 Are the CRQLs adjusted to reflect sample dilutions
and, for soils, % moisture? r ] __
ACTION: If errors are large, call lab for
explanation/resubmittal, make any
necessary corrections and document
effect in data assessments.
ACTION: When a sample is analyzed at more than
one dilution, the lowest CRQLs are used
(unless a QC exceedance dictates the use
of the higher CRQL data from the diluted
- sample analysis). Replace concentrations
that exceed the calibration range in the
original analysis by crossing out the "E"
value on the original Form I and substituting
it with data from the analysis of diluted
sample. Specify which Form I is to be used,
then draw a red "X" across the entire page
of all Form I's that should not be used,
including any in the summary package.
ACTION: Quantitation limits affected by large,
off-scale peaks should be qualified as
unusable (R). If the interference is
on-scale, the reviewer can provide an
approximated quantitation limit (UJ) for
each affected compound.
12.0 Chromatocrram Quality
12.1 Were baselines stable?
12.2 Were any electropositive displacement
(negative peaks) or unusual peaks seen?
ACTION: Address comments under System
Performance of data assessment.
- 51 -
-------
STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
YES NO N/A
13.0 Field Duplicates
13.1 Were any field duplicates submitted for
PEST/PCB analysis? r 1
ACTION: Compare the reported results for
field duplicates and calculate the
relative percent difference.
ACTION: Any gross variation between field
duplicate results must be addressed
in the reviewer narrative. However, if
large differences exist, identification
of field duplicates should be confirmed
by contacting the sampler.
- 52 -
-------
ATTACHMENT 1
SOP NO. HW-6 Page of
CLP DATA ASSESSMENT
Functional Guidelines for Evaluating Organic Analysis
Case No. SDG No. LABORATORY SITE
DATA ASSESSMENT:
The current Functional Guidelines for evaluating organic data have
been applied.
All data are valid and acceptable except those analytes which have
been qualified with a "J" (estimated), "N" (presumptive evidence
for the presence of the material), "U" (non-detects) , "R1*
(unusable) , or "JN" (presumptive evidence for the presence of the
material at an estimated value). All action is detailed on the
attached sheets.
Two facts should be noted by all data users. First, the "R" flag
means that the associated value is unusable. In other words, due
to significant QC problems, the analysis is invalid and provides no
information as to whether the compound is present or not. "R"
values should not appear on data tables because they cannot be
relied upon, even as a last resort. The second fact to keep in
mind is that no compound concentration, even if it has passed all
QC tests, is guaranteed to be accurate. Strict QC serves to
increase confidence in data but any value potentially contains
error.
Reviewer's
S ignature: Date: / /19 9_
Verified By: Date: / /199
-------
ATTACHMENT 1
SOP NO. HW-6 Page of
DATA ASSESSMENT
1. HOLDING TIME:
The amount of an analyte in a sample can change with time due to
chemical instability, degradation, volatilization, etc. If the
specified holding time is exceeded, the data may not be valid.
Those analytes detected in the samples whose holding time has been
exceeded will be qualified as estimated, "J". The non-detects
(sample quantitation limits) will be flagged as estimated, "J", or
unusable, "R", if the holding times are grossly exceeded.
The following analytes in the samples shown were qualified because
of holding time:
-------
ATTACHMENT 1
SOP NO. HW-6 Page of
DATA ASSESSMENT
2. BLANK CONTAMINATION:
Quality assurance ;(QA) blanks, i.e., method, trip, field, or rinse
blanks are prepared to identify any contamination which may have
been introduced into the samples during sample preparation or field
activity. Method blanks-mieasure laboratory contamination. Trip
blanks measure cross-contamination of samples during shipment.
Field and rinse blanks measure cross- contamination of samples
during .field operations, iff ^e dbncentration of >the ahalyte is
less than 5 times the. blank contaminant level ('l*p}"'t!imes -for the
common contaminants)> the analyses, are qualified as ^hpn-- detects,
"U". The following analytes in the samples shown were'qualified
with "U" for these reasons:
A) Method blank contamination
B) Field or rinse blank contamination ("water blanks" or
"distilled water blanks" are validated like any other sample)
C) Trip blank contamination
-------
ATTACHMENT 1
SOP NO. HW-6 Page of
DATA ASSESSMENT
3. MASS SPECTROMETER TUNING:
Tuning and performance criteria are established to ensure adequate
mass resolution, proper identification of compounds, and to some
degree, sufficient instrument sensitivity. These criteria are not
sample specific. Instrument performance is determined using
standard materials. Therefore, these criteria should be met in all
circumstances. The tuning standard for volatile organics is
bromofluorobenzene (BFB) and for semi-volatiles is
decafluorotriphenyl- phosphine (DFTPP).
If the mass calibration is in error, or missing, all associated
data will be classified as unusable, "R". The following samples
shown were qualified with "R" because of tuning:
-------
ATTACHMENT 1
SOP NO. HW-6 Page of
DATA ASSESSMENT
4. CALIBRATION:
Satisfactory instrument calibration is established to ensure that
the instrument is capable of producing acceptable quantitative
data. An initial calibration demonstrates that the instrument is
capable of giving acceptable performance at the beginning of an
experimental sequence. The continuing calibration verifies that
the instrument is giving satisfactory daily performance.
A) RESPONSE FACTOR
The response factor measures the instrument' s response to specific
chemical compounds. The response factor for the VOA/BNA Target
Compound List (TCL) must be > 0.05 in both the initial and
continuing calibrations. A value < 0.05 indicates a serious
detection and quantitation problem (poor sensitivity). If the mean
RRF of the initial calibration or the continuing calibration has a
response factor <0.05 for any analyte, those analytes detected in
environmental samples will be qualified as estimated, "J". All
non-detects for those compounds will be rejected ("R"). The
following analytes in the samples shown were qualified because of
response factor:
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ATTACHMENT 1
SOP NO. HW-6 Page of
DATA ASSESSMENT
5. CALIBRATION:
A) PERCENT RELATIVE STANDARD DEVIATION (%RSD) AND PERCENT
DIFFERENCE (%D):
Percent RSD is calculated from the initial calibration and is used
to indicate the stability of the specific compound response factor
over increasing concentration. Percent D compares the response
factor of the continuing calibration check to the mean response
factor (RRF) from the initial calibration. Percent D is a measure
of the instrument's daily performance. Percent RSD must be <30%
and %D must be <25%. A value outside of these limits indicates
potential detection and quantitation errors. For these reasons,
all positive results are flagged as estimated, "J"; and
non-detects are flagged "UJ". If %RSD and %D grossly exceed QC
criteria, non-detect data may be qualified "R".
For the PCB/PESTICIDE fraction, if %RSD exceeds 20% for all
analytes except for the 2 surrogates (which must not exceed 30%
RSD), qualify all associated positive results "J" and non-detects
"UJ".
The following analytes in the samples shown were qualified for %RSD
and %D:
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ATTACHMENT 1
SOP NO. HW-6 Page of
DATA ASSESSMENT
6. SURROGATES/ SYSTEM MONITORING COMPOUNDS (SMC):
All samples are spiked with surrogate/ SMC compounds prior to
sample preparation to evaluate overall laboratory performance and
efficiency of the analytical technique. If the measured surrogate/
SMC concentrations were outside contract specifications,
qualifications were applied to the samples and analytes as shown
below. The following analytes for the samples shown were qualified
because of surrogate/ SMC recovery:
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ATTACHMENT 1
SOP NO. HW-6 Page of
DATA ASSESSMENT
7. INTERNAL STANDARDS PERFORMANCE:
Internal Standard (IS) performance criteria ensure that the GC/MS
sensitivity and response are stable during every experimental run.
The internal standard area count must not vary by more than a
factor of 2 (-50% .to +100%) from the associated continuing
calibration standard. The retention time of the internal standard
must not vary more than ±30 seconds from the associated continuing
calibration standard. If the area count is outside the (-50% to
+100%) range of the associated standard, all of the positive
results for compounds quantitated using that IS are qualified as
estimated, "J", and all non-detects as "UJ" only if IS area is
< 50%. Non detects are qualified as "R" if there is a severe loss
of sensitivity ( < 25% of associated IS area counts).
If an internal standard retention time varies by more than 30
seconds, the reviewer will use professional judgment to determine
either partial or total rejection of the data for that sample
fraction. The following analytes in the samples shown were
qualified because of internal standards performance:
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ATTACHMENT 1
SOP NO. HW-6 Page of
DATA ASSESSMENT
8. COMPOUND IDENTIFICATION:
A) VOLATILE AND SEMI-VOLATILE FRACTIONS
TCL compounds are identified on the GC/MS by using the analyte's
relative retention time (RRT) and ion spectra. For the results to
be a positive hit, the sample peak must be within ±0.06 RRT units
of the standard compound/ and have an ion spectra which has a ratio
of the primary and secondary m/e intensities within 20% of that in
the standard compound. For tentatively identified compounds (TIC) ,
the ion spectra must match accurately. In the cases where there is
not an adequate ion spectrum match, the laboratory may have
provided false positive identifications. The following analytes in
the samples shown were qualified for compound identification:
B) PESTICIDE FRACTION:
The retention times of reported compounds must fall within the
calculated retention time windows for the two chromatographic
columns. The percent difference (%D) of the positive results
obtained on the two GC columns should be <25% The following
analytes in the samples shown were qualified because of compound
identification:
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ATTACHMENT 1
SOP NO. HW-6 Page of
DATA ASSESSMENT
9. MATRIX SPIKE/SPIKE DUPLICATE, MS/MSD:
The MS/MSD data are generated to determine the long-term precision
and accuracy of the analytical method in various matrices. The
MS/MSD may be used in conjunction with other QC criteria for some
additional qualification of data. The following analytes, for the
samples shown, were qualified because of MS/MSD:
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ATTACHMENT 1
SOP NO. HW-6 Page of
DATA ASSESSMENT
10. OTHER QC DATA OUT OF SPECIFICATION:
11. SYSTEM PERFORMANCE AND OVERALL ASSESSMENT (continued on next
page if necessary):
12. CONTRACTUAL NON-COMPLIANCE:
13. This package contains re-extraction, re-analysis or
dilution. Upon reviewing the QA results, the following form
I(s) are identified to be used:
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ATTACHMENT 1
SOP NO. HW-6 Page of
DATA ASSESSMENT
11. SYSTEM PERFORMANCE AND OVERALL ASSESSMENT (continued):
-------
SOP NO. BR-7
Revision # 3
TCLP DKIA VMJEKTICN
Leon Tp7?T^s/<^yJJann>entalScientist
Toxic and Hazardous 'Waste Section
BY:
Toxic and "hazardous Waste Section
• ) • 1 (\ D
CONCURRED BY; 'KLgY/V Uj -^ iNJM^ Date: w
AEEKJ7ED BY:
Monitoring Management Branch
-------
ALL LAND BAN TCLP ANALYSIS MOST USE SW-846 METHODS.
IHIS SOP ONLY APPRAISES THE' TCLP EXTRACTION PROCEDURE. TO COMPLETELY VAUDAE A
TCLP ANALYSIS, YOU MUST ALSO USE THE EEGION II SOPS FOR ORGANIC AND INORGANIC DA£P>
VALIDATION.
BEFORE VALIDATING TCLP 'DATA, THE DATA' VALIDATOR MUST DETERMINE IF ANY TOXECTTY
CHARACTERISTIC OR LAND BAN REGULATORY ACTION LEVELS ARE APPLICABLE.
YES NO N/A
Was a ZHE vessel used for VOAs? [ ]
Was there any evidence of leakage?
Action: If a ZHE vessel leaked, or was not used,
reject (R) all- VOA data, except data which
exceeds the regulatory level for any analyte.
See attached list for TC regulatory levels.
If other analytes are being validated, the validator
most determine which, if any, Land Ban regulatory
levels are applicable. The Land Ban TCLP
regulatory levels are listed in 40CFR268.
Did the lab use proper bottles? [ ]
Action:" If a plastic bottle was used, except for PTFE,
reject (R) all non detect organic data. All positive
organic values should be flagged as presumptively present
at an estimated quantity (JN).
Did the lab correctly compute % solids? [ ]
Action: If the lab made an error, request revised data.
If appropriate, did the lab reduce particle size? [ ]
Action: If the lab did not perform a required
particle size reduction, reject (R) all non detects.
All positive values should be flagged as
presumptively present at an estimated quantity (JN).
Was the correct extraction fluid used? [ ]
Was the pH of the extraction fluid correct? . [ ]
(4.88-4.98 for fluid #1) (2.83 - 2.93 for
extraction fluid #2)
Action: If the extraction fluid pH was wrong, or the
wrong fluid was used, reject (R) all nan detects.
All positive values "should be flagged as presumptively
present at an estimated quantity (JN).
-1-
-------
YES NO N/A
Was the correct weight of extraction fluid used? [_ ]
Action: If the extraction fluid weight is not +15%
of the correct value, flag all results as estimated (J).
If the extraction fluid weight is more than 30% above
the correct value, reject (R) all non detects, and
flag all positive values as presumptively present at
an estimated quantity (JN).
For volatile analytes, was the sample weight 25
grams or less? [ ]
Action: If the sample weight is more than
25 grams, flag ail data as estimated (J).
Were the TCLP extracts properly preserved? [ ]
(Metals must be preserved to a pH <2 with HNOj).
Action: If the preservative causes precipitation,
the sample should not be preserved, but the sample
should be analyzed as soon as possible after
extraction. The use of organic preservatives is optional.
If proper inorganic 'preservation procedures were not
followed, reject (R) all non detects, and flag all
positive values below regulatory action levels as
presumptively present at an estimated quantity (JN).
Positive data at concentrations above regulatory
action levels should not be qualified.
Is there a TCLP blank with the appropriate TCLP [ ]
fluid for every 20 samples? (This is in
addition .to the method blanks, which are required
for each analytical method).
Action: If there is no TCLP blank, call laboratory
for explanation/resubmittal. If not available,
reject (R) all associated positive data.
Contaminants in TCLP blanks should be
treated as method blank contaminants when validating
data.
Have samples been analyzed within TCLP holding
times from date, of collection ? [ ]
f
NOTE: CLP holding times do not apply to TCLP analysis.
Tne following table lists TCLP holding times:
-2-
-------
TCLP Holding Times
TCLP HOLDING
TIMES (DAYS)
VOA
ORGANIC
EXIPACIABLES
MERCURY
OTHER METALS
FRCM COLLECTION
TO TCLP EXTRACTION
14
14
28
180
FROM TCLP EXTRACTION
TO PREPARATIVE
EXTRACTION
N/A
7
N/A
N/A
FROM PREPARATIVE
EXTRACTION TO
ANALYSIS
14
40
28
180
HOLDING TIME DECISION TABLE
Have samples been analyzed within TCLP holding time?
If Yes.
Action: Do not qualify data because of holding time.
If No. ......
Action: In the sample, does any analyte exceed the regulatory level?
Toxicity Characteristic regulatory action levels are listed on page 5 of this SOP.
The Land Ban regulatory action levels are listed in 40CFR268.
If No.
Action: Reject (R) all
analytes.
If Yes.
Action: Do not qualify
analytes which exceed
regulatory levels.
Mention in data
assessment that
reported value
represents the
minimum concentration
present.
Assume that TCLP analysis of TC analytes is for the purpose of determining
compliance with the TC regulatory levels (attached). If other analytes are being
validated, the validator must determine which, if any, land Ban regulatory levels
are applicable. The, Land Ban TCLP regulatory levels are listed in 40CFR268.
-3-
-------
ANALYTICAL DATA. MUST BE VALIDATED ACCORDING TO THE REGIONAL ORGANIC AND INORGANIC.
DATA VALIDATION SOPS BEFORE THE FOLLOWING QUESTIONS MAY BE ADDRESSED.
YES NO N/A
Have any acetates, acetic acid, or acetic anhydride
been reported as TICs? _ [ _ ] _
Action : If yes, reject (R) TICs.
Are all organic oanpounds analyzed by the TCLP method .
properly calibrated? '[_ _ ] _ _
Analytes on Form I that have not been calibrated should
be qualified as • follows: non-deteets .should be
rejected .(R)'; positive values should , be reported as
TICs, and/flagged "
Have multi-phasic saitples been properly analyzed?
(Check to see if aqueous sanples .Mye >. .5% solids.)
If not/ .reject (R) ";ail data .below 'regulatory action
levels.
Have adequate raw data deliverables been submitted?
Action: If not, contact the laboratory.
If the raw data is not available,
use professional judgement to guilify analytical
data, arid mention in data assessment.
Was the method of standard additions properly [ _ ] _ _
utilized for analysis of metals?
Action: If not, all metals data should be
qualified as estimated "J".
THE POLDDRING STATEMENT HOST BE ADDED TO ALL TCLP DATA VALIDATION KEPORTS:
'» ---.-- • _ - -
m
Analytical data qualified as "JN11 or "R" may not be used to detnonstrate conpliance
with Toxieity Characteristic :or land-Ban Reguiations.
-4-
-------
TC ANALYSES AND THEIR REGCIATORY LEVELS
Regulatory
constituent Level (ncr/1)
benzene
carbon tetrachloride
chlordane
chloroibenzene
chlorof ora
o-cresol
m-cresol
p-cresol
1 , 4-dichlorcbenzene
1 , 2-dichlorcethane
1, 1-dichloroethylene
2 , 4-dinitrotoluene
heptachlor
arsenic
barium
cadmium
c* T^ *mm i \TK\
lead
mercury
selenium
0.5
0.5
0.03
100.0
6.0
200.0
200.0
200.0
7.5
0.5
0.7
0.13
0.008
5.0
100.0 "
1.0
5.0
5.0
0.2
1.0
Constituent
Regulatory
Level (ma/1)
hexacMorcbenzene 0.13
hexachloro-1,3-butadiene 0.5
hexachloroethane 3; 0
methyl ethyl ketone 200.0
nitrobenzene 2.0
pentachlorophenol 100.0
pyridine 5.0
tetrachloroethylene 0.7
trichloroethylene 0.5
2,4,5-trichlorcphenol 400.0
2,4,6-trichlorophenol : 2.0
vinyl chloride 0.2
silver 5.0
endrih "" 0.02
lindane 0.4
iDethoxychlor 10.0
toxaphene 0.5
2,4-D 10.0
2,4,5-TP (silvex) 1.0
-5-
-------
•o
CD
D
Q.
x'
<
-------
Appendix V
References for Multi-phasic and Oily Waste
-------
United States
Environmental Protection Agency
Workshop on
Predicting the Environmental
Impact of Oily Materials
July 14, 1992
Eighth Annual Waste Testing
And
Quality Assurance
Symposium
Arlington, VA
-------
PREDICTING THE ENVIRONMENTAL IMPACT OF OILY MATERIALS:
INTRODUCTION AND REGULATORY PERSPECTIVE
David Friedman
USEPA Office of Research and Development
401 M Street SW
Washington, DC 20460
BACKGROUND
Prevention of groundwater contamination has historically been one of the EPA's
highest priorities in implementing the RCRA program. To that end/ the Agency has
developed and promulgated test methods, fate and transport models/ and regulatory
standards to control the management of wastes whose properties might pose a hazard to
groundwater. Scientists axe concerned with ofly waste due to its volume, toxicity, and
potential for causing severe ecological damage. Such wastes take many forms including:
liquids of widely varying viscosity, contaminated soils, sludges, and tarry "plastic" masses.
Oily wastes have some unique properties. They can migrate like a liquid but appear
to be a solid. Because they result from many commercial processes and applications, they are
broadly distributed, of very large volume, and of tremendous commercial importance.
In developing the hazardous waste identification characteristics, EPA highlighted its
concerns with protecting ground water resources by developing the Extraction Procedure
Toxicity Characteristic (40 CFR 26124). The characteristic relies on laboratory procedures to
predict toxicant mobility.
Over the years a number of laboratory extraction methods have been applied to the
problem of predicting what might migrate from ofly wastes managed under landfill
conditions. Among the test methods mat have been developed and employed to identify
those wastes which might pose an unacceptable hazard are: EPA methods 1310,1311 and
1330 (Extraction Procedure, Toxicity Characteristic Leaching Procedure and Oily Waste
Extraction Procedure).
The current approaches all have deficiencies with respect to predicting the mobility of
toxic chemicals from ofly wastes. Methods 1310 (EP) and Method 1311 (the TCLP)
underestimate the mobility of many oily wastes due to filter dogging problems, their
precision is less than desirable, and they have certain operational problems. Conversely,
Method 1330 (OWEP) probably overestimates mobility since it emulates a worst possible rase
scenario. None of the available laboratory mobility procedures is thus totally satisfactory.
Presented mjtity 14,1992 at EPA Wwfctopff Pagel
on "Piuitctmg On EiwuviuiitiUul Impact of OSy Materials"
Printed on Recycled Paper
-------
PROBLEM
Given the importance of this issue/ it is imperative that accurate/ precise, and usable
approaches to characterizing the mobility of oily materials be developed. That is what we
are here for today.
The problem of mobility estimation is too large and complicated for us to try and
solve all its aspects in a half day. Therefore/ we win focus on just one aspect of the
problem - predicting the initial source term. To put it another way, we want to predict the
highest concentration of material that might be released from the waste to the soil
immediately below the point of disposal for some reasonable amount of time. This
information would then feed into the fate and transport models used to predict the final
toxicant concentration at some distance away from the disposal area.
DISPOSAL SCENARIO OF CONCERN
The priority waste management facility scenario mat EPA has selected to be modeled
in this workshop is placement of the waste into or on the ground (e.g., landfill or lagoon).
Within this scenario a number of parameters need to be considered. These include:
TV*! i i i y IYI \ ^ITP
Rainfall regime,
Biodegradation/
Hydrolysis/
Soil types (ageimnp sofl. underlying the waste management unit has a
porosity similar to that of sand)/ and
Amount of waste (assume amount is large enough so that it can be
considered to be infinite).
FATE AND TRANSPORT MODEL CONSIDERATIONS
To properly manage oily wastes to protect ground water sources from contamination
by waste constituents/ an adequate model to predict the fate and transport in the subsurface
environment is needed. The Agency is developing a model to simulate the migration of
aqueous and nonaqueous phase liqnidg and the transport of individual rtw»mirai constituents
which may move by convection and dispersion in each phase.
As input parameters/ the model needs information on the amount and composition of
both the aqueous and nonaqueous phase liquid portions of the waste as well as the
composition of the leachate that might be generated by action of surface waters on any
Presented on July 14, 1992 at EPA Workshop n Page 2
on rrc&zczzntg inc £mwi>jiiiiCJiiui Jffiptcf of Otty Mtttcnus
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"solid" material that may have initially been present in the waste material At this time, the
Agency does not have a precise way of denning either an "aqueous phase liquid" or a
"nonaqueous phase fiquid".
REGULATORY PERSPECTIVE
In an ideal situation, an effective approach to evaluating oily wastes would:
• Be simple to use (not require sophisticated equipment, nor constant
attention by a highly trained technician),
• Be inexpensive to run,
• . Take as little time as possible to perform (ideally no more than 24
hours),
• Be accurate (relative to predicting behavior of waste in the
environment),
• Be precise (Le., be reproducible),
• Be rugged (capable of characterizing a broad range of waste types and
constituents of concern), and
• - Not generate wastes (e.g., generate little if any solvent waste and waste
contaminated media).
The characteristics mat the approach should have (maximum desirable values for each
parameter) are:
• A high degree of freedom from false negatives (any errors tend toward
overestimation of threat to environment),
• Precision (RSD <50%),
• Relatively low cost,
• Taking as little time as possible to perform (<24 hours), and
• Ruggedness.
Presented an Jvfy 14,1992 at EPA Worktop U Page 3
on "Pifdifling the Eiwuoiuutuiol Impact of OSy Materials "
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OPTIONS FOR CONSIDERATION
I. Develop a two-component mobility test that determines the fraction of the
waste which is flowabk (capable of physical movement under the influence of
gravity and overburden pressure) under the conditions of the test Suggested
conditions: room temperature and 50 psL Define as mobile an material that is
flowable under terms of the test phis the aqueous extract of the non-flowable
fraction. Under this option/ the procedures used are independent of waste
properties and disposal environment
IL Develop a Dingle generic laboratory procedure to estimate what disposal point
concentration would result from aqueous leaching of the hazardous
constituents from both the mobile and non-mobile fraction of the material
Under this option/ the procedures used are independent of waste properties
and disposal environment
IIL Employ a series of laboratory test procedures to evaluate the waste material.
These procedures would be keyed to the fate and transport model to be
employed to evaluate the data. The procedure also would be independent of
the properties of the material under evaluation.
The questions we would like you to address are:
• What would be the "best" approach to use in order to predict the nature
and concentration of the components that would leach from oily wastes
if the waste were to be placed in an unlined lanrffiji environment?
• If the necessary tools are not presently available/ how should such a
test method or model be developed and evaluated?
• What form should a cooperative development program take? How
could it be organized? Who might the cooperators be? How long
would you expect it to take to develop the necessary tools?
If you think of any ideas/ information, or suggestions mat you feel the Agency should
consider when addressing this issue, please send them to us. Send your comments to:
David Friedman
US Environmental Protection Agency
401 M St SW (RD-680)
Washington, DC 20460
We wifl need to receive your comments by August 21,1992 in order for them to be
incorporated into the conference final report
Presented on Jufy 14,1992 at EPA Wor&upn Page 4
on "Predicting the Ernrirmaaattal Impact of OSy Materials"
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PREDICTING THE ENVIRONMENTAL IMPACT OF OILY WASTE:
INDUSTRY PERSPECTIVE
Clifford T. Naiquis
BP Research
4440 Warrensvffle Center Road
Cleveland, OH 44128-2837
STATEMENT OF ISSUE
Managing solid waste in an environmentally sound manner is a subject of high
concern to industry, EPA and the public However, we must have regulatory tools which
accurately reflect the environmental hazard, and analysis tools which accurately assess the
potential impact of various management approaches. We need to bring the best science to
bear on the evaluation of the potential environmental threat from oily waste disposal,
considering the likely management scenarios. One way EPA has decided to regulate certain
oily waste in the past is by listing the waste as hazardous under RCRA. This approach
identifies a material as an environmental threat based on possible (but not necessarily
realistic) mismanagement scenarios. A second way to regulate the waste is to determine if it
is hazardous using the toxicity characteristic CTO and the Toxirity Cha^acterisHfs Leaching
Procedure (TCLP) test This test is used to determine whether a waste is hazardous or not
based upon a specific leachabflity test and municipal landfill disposal scenario. The options
explored in this paper serve to promote thinking about new approaches for identifying the
environmental threats and thereby to better focus regulations dealing with the management
of these materials. This will be done by introducing and critiquing current most common
predictive methods and presenting potential avenues for more accurate methods.
Although it is nearly impossible to precisely define the term "oily waste", the
following analysis can provide a basis for further discussion:
a) An oil is generally an immiscible or relatively insoluble liquid, varying in
composition but consisting of organic constituents. Petroleum oils principally
consist of hydrocarbons; vegetable and animal oils are glycerides, and fatty
*;; and essential oils are terpenes, alkaloid^
b) An ofly waste is an industrial process waste or residual bearing oil in visual
and/or measurable proportions.
c) Oil in oily wastes can occur in any matrix, including: sorbed to dry solids; in
sludges or shinies; multi-phase liquids or sludges/shinies with multi-phase
Presented on July 14, 1992 at EPA Workshop n Page 5
on "Predicting Ac Eiwuuninfiitul trnpoct of OSy Uotenols"
-------
liquids, if water is present Proper treatment and disposal of all such matrices
is a concern of the petroleum industry.
d) Analysis of oils in oily wastes can be accomplished by techniques such as Total
Petroleum Hydrocarbons (TPH) (not constituent-specific) or TCLP (constituent-
specific). m a number of contexts, the procedures of methods such as these
serve to dpfap what is meant by "oil" and "oily waste."
e) Oily wastes possess a wide variety of compositions and physical and
toxicological properties.
Some examples of oily waste include petroleum refinery sludges, such as oil- water
separator sludge and dissolved air floatation from, storage tank bottom sludge, used oil and
others. Expanded beyond the petroleum community mere are many types of oily wastes
(POTW sludges, polymer plants, timber processing, iron and steel pulp and paper, meat
packing, slaughterhouse, leather tanning, coH coatingjestaurants, and miscellaneous foods
including meat, dairy and vegetable based oils and fats, etc).
Currently mere are a variety of state and local programs designed to address potential
environmental impacts of the management of various types of ofly materials, such as E&P
wastes, spill residues and U5T wastes. A number of RCRA listed and toxicity characteristic
wastes are also regulated under federal programs. EPA is currently evaluating the possible
listing of a&ditiapa\ petroleum refining wastes.
Unfortunately, the current analytical methods for determination of the environmental
threat of petroleum constituents in wastes and. ofly materials via the TCLP test and model
and RCRA listing system remain controversial. USEPA, arademia, and the regulated
community are continuing efforts to identify a sound, reproducible methodology to
accurately assess these threats. In fact, EPA has recently proposed a rule to address the over-
regulation of listed wastes created by EPA's "mixture" and "derived-from" rules. This
initiative, called the Hazardous Waste Identification Rule, could have major impacts on the
classifications and management of hazardous and nonhazardous industrial wastes, including
oily waste.
An approach that the American Petroleum Institute (APD has suggested to the
Agency is concentration-based exclusion criterion coupled with contingent management It is
a two-tiered process for determining whether wastes captured under the RCRA fisting rule
should or should not continue to be regulated as hazardous. One tier would allow wastes
with constituents below health based levels (with an appropriate multiplier to account for
dilution and attenuation) to be deemed nonhazardous provided the waste does not exhibit a
RCRA characteristic. A second tier would allow wastes that contain constituents below
somewhat higher health based levels to be deemed as nonhazardous, provided these wastes
are managed in certain environmentally protective ways. This second approach would alter
the current system by basing a waste's classification on how it is actually managed and not
how it could be hypothetically mismanaged.
Presented on ]uly 14,1992 at EPA Workshop II Page 6
an "Predicting the Eiwuoiuauilul Impact of O3y Materials"
-------
On the test method side, many, including Environment Canada, ASTM and the
USEPA, have been involved with the development of improved teachability and contaminant
fate/transport tests and models. Despite this work, predicting the potential environmental
hazard associated with oily wastes remains problematic
TCLP APPROACH
The toxiory characteristic leaching procedure (TCLP) was developed as a way to
evaluate the threat of solid waste disposal under "-a mismanagement scenario for toxic
wastes which constitutes a prevalent form of improper management-namely, the co-disposal
of toxic wastes in an actively decomposing municipal landfill which overlies a groundwater
aquifer™" (Fed. Reg., May 8,1990). The TCLP is a leaching and aririir aqueous extraction
test The test was designed to model mismanagement of the disposal of process wastes. The
Toxjcity Characteristic (TO rule itself, and constituent-specific limits associated with the TC,
define wastes as hazardous on the basis of the concentrations of certain toxic constituents.
The TC and its constituent-specific limits were developed in large part to protect human
health from contamination of drinking water aquifers. The TCLP test, as currently
interpreted, is applicable to those wastes which produce a separate non-aqueous phase as
well as those which do not
Specifically the model system that forms the Haste for the regulatory limits imposed
by the current toxicity characteristic is one which assumes mat the waste is disposed of in a
municipal hazardous waste lanHfin where it is leached by aH^if landfill liqm^ emerges
from tiie landfill bottom into underlying groundwater whereupon it migrates to an
hydiauHcally down-gradient drinking water well (see Figure 1).
The current Toxicity Characteristic defined-method for determining environmental
risks uses a three-part system, consisting of a physical model (TCLP), coupled to a
mathematical model (EPACML), coupled to a lexicological model The TCLP simulates
constituent leaching from a landfill, EPACML simulates constituent transport from a landfill
to a drinking water weH, and the lexicological model relates drinking water concentration to
health-effects. The TCLP was not designed as, and fails as, a multi-phase model This is
because the oil phase is simply treated as water. Additionally any multi-phase capability
within EPACML was ignored due to the TCLP output
Presented m July 14,1992 at EPA Workshop U Page 7
m "Predicting Hie Ermrmmattal impact of OQy Materials'
-------
- !
r
a
Toxicologlcal
models
QroundiDBter
i
Figure 1: Components of TC "System"
-------
Significant technical aspects of the TCLP simulation can be summarized as follows
(see Figure 2).
• No vadose zone-bottom of the landfill is in direct contact with the ground
water.
• The disposal of waste liquids (oil and water) are equally mobile.
• The liquids are not leached or diluted but ehite directly from the landfill into
the ground water.
• Infinite source-liquids continue to be released forever regardless of amount of
liquids in the original waste.
• The solids are leached with a 20:1 volume of acidic landfill leachate" which
then enters the ground water.
• Infinite source - the hazardous constituent concentration in the initial 20:1
leachate volume continues to be leached from the material forever, regardless
of mass of constituents in the original waste.
The linitiric and leachate travel through the ground water to a drinking water
well. Attenuation and dilution reduce concentrations by a factor of 100.
Oil moves as water.
Hazardous constituent concentrations achieve steady-state in the well at which
time the well-owner drinks two-liters/day for 70 years (oil and all).
VALIDITY OF THE TCLP APPROACH
Oily wastes provide a great challenge to those charged with evaluating their potential
impact on the environment Unfortunately the design of the TCLP test in concept/
methodology .and fate/transport modeling, inaccurately predicts the behavior of waste
containing separate-phase oil and organic constituents. One shortcoming is that it forces a
generic disposal scenario which may be reasonable for some cases but impossible for others.
Specific problems include operational problems with the test procedure, the assumption that
oil behaves identically to water in the environment, the validity of the disposal scenario, and
invalid contaminant fate/transport assumptions.
Presented mjuty 14,1992 at EPA Workshop n Page 9
on "Predicting &te Environmental bnpoet of O&y Materials"
-------
Landfill
I. no vadbee zone
2. flqueous and non-aqua
liquida treated identically
3. Liquids not leached or diluted
prior to entering groundurater
9. Individual
drlnke 2 L/dag
lor 70 geara
4. Infinite source
of waste liquids
5. Leachate enters
groundmater directly
20:1
acidic
leachate
Both
liquids
and
leachate
migrate
to moll
B. Infinite source
of leachate
7. Straight dilution 6
attenuation bg factor
of 100
B. Oil moves as mater
Figure 2: IBBUBB inherent in TC ecenerio which work to
introduce inaccuracy.
-------
The test system was not designed for multi-liquid phase materials. This results in
operational problems with me TCLP methodology including non-reproducible free oil
breakthrough, filter dogging/ and difficulties with volatiles equipment The zero headspace
extractor (ZHE) test equipment is difficult to clean. Some volatile chlorinated compounds are
transformed within the TCLP extraction (Bricka, et al, 1991). EPA has, to date, not provided
approved test methods which are validated for the analysis of metals in non-aqueous liquids
(55 FecLReg. 4444).
One of the initial steps in the TCLP test is pressure nitration of the waste For some
oily wastes/ non-aqueous liquid may be expressed. This liquid is segregated from the
remaining solids which are then acid-leached This a<*id leachate is combined with the non-
aqueous liquid to produce the TCLP leachate" which is compared to
criteria.
Implicit in this procedure is the assumption mat both aqueous and non-aqueous
liquids will behave identically, both within the landfill and upon their hypothetical release.
EPA has been able to provide little, if any, support for this rritiral portion of the TOP.
"The initial liquid/solid separation problems are due to the tendency for some material,
such as certain types of oily wastes, to clog the 0.45um filter and prevent filtration.— This
problem is serious, since materials which do not pass the 0.45 um filter are treated as solids
even if they physically appear to be a liquid. These (liquid) wastes are then carried through
EP extraction as a solid."
This is particularly serious for oily wastes, since oils have been known to frequently
migrate to ground waters. It is important for the liquid (sid/soBd separation to treat/ as
liquids, those materials which can behave as liquids in the environment"
"As indicated below, EPA believes mat the liquid/solid separation technique—
reduces variability — and that it also provides a more adequate differentiation between those
materials that behave as liquids in the environment, and those materials which behave as
solids."(51 Fed. Reg. 21658)
As we gain experience with risk evaluations, we see that the risk posed by light, non-
aqueous phase liquids (Le. "oil") appears to be mostly due to dissolved contaminants in
drinking water. The calculated risk due to free oil is not great due to the lack of exposure.
As it moves through the soil, oil win be immobilized in the soil and from mat point may
partition into me water phase according to constituent solubilities. Any mobile oil migrating
to a water weH does not represent a 2L/day, 70 year hazard since it is not realistic to project
that anyone win drink free-phase hydrocarbons daily for their entire lives. Therefore, it
makes some technical sense to leach the oil fraction with the aridir medium along with the
solids.
Presented on July 14,1992 at EPA Worktop n Page 21
on "Predicting the EtwuuniittJitul Impact ofOSy Materials"
-------
The disposal scenario as depicted by EPA is not an accurate description of current
waste disposal practices. An EPA-O5W survey, several years old already, documents that
liquid-type wastes are no longer being accepted by municipal landfills (51 Fed. Reg. 21655).
New test methods based upon actual waste management situations would give more
accurate results than those based on generic hypothetical scenarios.
Industry has commented upon the shortcomings of the current TCLP/CML model
For example, the infinite source assumptions require contaminant mass to continue to be
available for introduction into ground water until steady state is achieved. This is
listic One improvement would be to design transient, declining source terms into the
model. Further, there is no consideration of a vadose zone although we know it exists and
future fcndfifl regulations wfll require the presence of a vadose zone. The TCLP is not
designed to handle the separate organic phase flow. The current TCLP system does not take
into account aerobic biodegradation, volatilization, or retardation. Hydrolysis is apparently
being considered at this juncture, but is not currently part of this system.
The unilateral application of TCLP to multi-phase wastes, especially those containing
oily materials, is unsupported and inappropriate. There is no evidence that non-aqueous
liquids behave as aqueous liquids in a landfill Indeed, such liquids have an affinity for the
solid materials in the landfill which could cause contaminants to be less mobile than
predicted by the TCLP.
Until work on the behavior of non-aqueous materials and the prediction of their
movement is more mature, the non-aqueous liquids should be treated like the waste itself
and be subjected to the same extraction with ariHir fluid. To the extent that hazardous
constituents are released into the extractant, they should be combined with the aqueous
extract generated from the waste solids.
THE EFFECTS OF THE CURRENT TC SCENARIO MODEL - SOME IMPACTS
A number of wastes from the petroleum industry, such as waters from tank
drawdowns, ground-water extraction, and hydrotesting, are or may be subject to the TC rule
even though there is no conceivable way that these materials would ever find their way into
alandfOL
The RCRA Corrective Action Program could potentially generate large quantities of
petroleum-contaminated soils. On-site and in-situ management techniques are not accurately
represented by the TCLP. In addition, a number of states currently have effective response
programs for clean up of spills and other releases of petroleum into the environment States
are concerned that application of the TCLP (particularly if TCLP is a poor estimator of
environmental threat) will seriously impact operation and effectiveness of these programs by
adding unnecessary and unwarranted hazardous waste handling requirements to wastes
which don't pose a threat We can no longer afford to waste large sums of money handling
solid waste in a manner which over estimates the actual environmental threat
Presented on July 14,1992 at EPA WoriskopH Page 12
on "Predicting Ac EiwuuiuniMlid input of OSy Mtttsnols"
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A WAY FORWARD - SAB LEACHABIUTY SUB COMMUTE
Given the problems with the applicability of the TCLP to multi-phase waste/ are there
any alternatives? What are the potential ways forward?
Last year, a report was issued by the Science Advisory Board (Environmental
Engineering Committee/ Leachabih'ty Subcommittee), entitled "Recommendations and
Rationale for Analysis for Contaminant Release." It contained nine recommendations:
• A variety of contaminant release tests and test conditions which in corporate
adequate understanding of the important parameters that affect leaching
should be developed and used to assess the potential lease of contaminants
from sources of concern.
• Prior to developing or applying any leaching tests or models, the controlling
mechanisms must be defined and understood.
• A consistent/ repeatable and easily applied, physical, hydrologic and
geochemical representation should be developed for the waste management
scenario of concern.
• Leach tests and conditions (stresses) appropriate to the situations being
evaluated should be used for assessing long-term contaminant release
potentifll-
• Laboratory leach tests should be field-validated/ and release test accuracy and
precision established before tests are broadly applied.
• More and improved leaching models should be developed and used to
complement laboratory tests.
• To facilitate the evaluation of risk implications of environmental releases/ the
Agency should coordinate the development of leach tests and the development
of models in which release terms are used.
• The Agency should establish an inter-office, inter-disciplinary task group,
including ORD to help implement these recommendations and devise an
Agency-wide protocol for evaluating release scenarios, tests, procedures/ and
their applications.
• The task group should also be charged with recommending what me
appropriate focal point(s), responsibilities, and organizational, budgetary and
communication links should be within the Agency for the most effective/
continued and ongoing support and pursuit of research/ development/ and
utilization of methods and procedures.
To fully accomplish an of the recommendations will be costly and time- consumii
ver there can be no alternate to core research on contaminant release and transport
Presented an July 14,1992 at EPA WwbtopH Page 13
on 'Predicting tite Enuiioiunatial Impact of OSy Materials"
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methods. SAB identified approximately 30 leach tests which are used internationally to
attempt to evaluate environmental threat of wastes. Unfortunately SAB concludes that each
method suffers from shortcomings.
APPLICATION TO OILY WASTE
If we wish to improve upon the system, there are two basic options:
1. Stick with the physical/mathematical model basis of the TCLP and improve
accuracy by modeling multi-phase transport and remove assumptions
predicated on long-term human consumption of immiscible product
2. Replace with a single alternative model/ either physical or mathematical.
We understand that EPA is exploring various enhanced modeling systems for multi-
phase disposal scenarios. These would include multi-phase flow within the unsaturated zone/
and partitioning between aqueous/ ofl/ and air phases within the soil Also included would
be saturated zone groundwater pollutant transport models which are more accurate. Industry
favors these developments as tools to better understand ofly waste disposal impact
On the other hand/ we must currently deal with an inappropriate TC rule. Currently,
industry must comply with the TC rule/ which means it must run TOP tests on oily wastes.
This has resulted in a disastrous situation. The TCLP was not designed to accurately assess
the environmental threat of ofly materials. Therefore it does not However, decisions on the
"proper" management of these wastes are being made on the basis of a flawed test
Industry has had to deal with the TC for many years. We have modified our waste
management approaches and strategies, we have complied with TC and land disposal
requirements and we are preparing to fully comply with Corrective Action. Unfortunately,
changes to the TC at this point may be just as disruptive and costly as compliance with the
TC has been to date. Modifications must be done carefully and deliberately, always using
the best possible science to ensure accuracy, not just consistency.
API supports, as mentioned in the Statement of Issue section, a concentration- based
exclusion coupled with contingent management for exempting listed hazardous waste from
\vouJo. ^dor^ss tine Tri
incorporating elements of actual management approaches instead of one hypothetical
approach.
The regulated community has volunteered to work with EPA bom as individuals/
individual companies/ and through trade organizations. We will continue to offer such
assistance. For myself, I see continued interaction between EPA- OSW and the American
Petroleum Institute Typical industrial support to EPA includes offering technical comment,
procuring wastes, providing waste generation and characterization data, and participating in
round-robin testing of new methods.
Presented on July 14,1992 at EPA Workshop n Page 14
on "Predicting the ETtmnraaentttl Impact of Ofly Materials"
-------
TABLE 1 - EXTRACTION TESTS
STATIC TESTS (LEACHING FLUID NOT RENEWED)
A. AGITATED EXTRACTION TESTS
TEST METHOD
LBACHINO FLUID
LIQUID.SOUD RATIO
MAXIMUM PARTICLE 5EB
NUMBER OF
EXTRACTIONS TIME OF EXTRACTIONS
TCLP(UII)
I
BPTOX(mO)
ASTM D3987-85
CALIFORNIA WET
LEACHATB EXTRACTION
PROCEDURE (MOE.
ONTARIO)
QUEBEC R.S.Q
(MOE. QUEBEC)
FRENCH LEACH TEST
(AFMOR. FRANCE)
EQUILIBRIUM
EXTRACTION
(ENVIRONMENT CANADA)
MULTIPLE BATCH
LEACHINO
PROCEDURE
(BNVmONMBNTCANADA)
ACBTICACID
0. IN ACETIC ACID
SOLUTION, pit 2.9.
FOR ALKALINE WASTES
O.I M SODIUM ACBTATB
BUFFER SOLUTION. pH 5.0.
FOR NON ALKALINE WASTES
0.5 N ACBTICACID
(pll'5.0)
ASTM TYPE W RBAOBNT WATER
0.2 M SODIUM OTRATE
(pH=5.0)
ACETIC ACID
2 MBQ/0
INORGANIC 0.02 MEQ/0
ORGANIC DISTILLED WATER
Dl WATER
DIS11LLDD WATER
ACETIC ACID
BUFFER, pH 4.5
2(1:1
9.3mm
IB HOURS
16:1 DURING EXTRACTION
20:1 FINAL DILUTION
20:1
10:1
20:1
10:1
4:1
4:1 OR
2:1
9.5mm
AS IN ENVIRONMENT
2.0 mm
AS IN ENVIRONMENT
GROUND
9.3mm
GROUND
9.3mm
VARIADLF.
24 HOURS
IS HOURS
41 HOURS
24 HOURS
24 HOURS
16 HOURS
7 DAYS
)4 HOURS
-------
TABLE I • EXTRACTION TESTS (continued)
S TESTMBTHOD
a
f [3 MATBRIALCHARACTER.
h, •*• 1ZATION CENTRB-4
{(MATERIAL CHARACTER.
IZATION CENTRE)
OILY WASTE
|j ^ (1330)
f SYNTHETIC PREC1PI-
3 TATION LBACHINO
gl PROCEDURE (1312)
EQUILIBRIUM
LOACH TEST
LBACHINO FLUID
CHOICE
SOXLBT WITH THF AND
TOLUENE BP ON
REMAINING SOLIDS
VARIABLE
DISTILLED WATER
I
LIQUID:SOUD RATIO MAXIMUM PARTICLE SIZE
10:1 2 FRACTIONS
74: 149mm
1000:300 Ml. 9.5mm
20:1
20:1 9.5mm
4:1 150 urn
NUMBER OP
EXTRACTIONS TIME OF EXTRACTIONS
1 20 DAYS TO
10 YEARS
150 -425 mm
3 24 HOURS (BP)
1 II HOURS
1 7 DAYS
B. NON-AGITATED EXTRACTION TESTS
TESTMBTHOD
STATIC LEACH
TESTMBTHOD
(MATERIAL CHACTBR-
ISTICCBNTRB-I)
HIGH TEMPERATURE
STATIC LBACH TOST
LBACHINO FLUID
CAN BE SITE SPECIFIC
SAME AS ABOVE
BUTATIOO°C
LIQU1D.SOUD RATIO MAXIMUM PARTICLE SIZE
VOL/SURPACB 10 urn 40 mm2 SURFACE AREA
VOL/SURFACB 10 urn 40 mm1 SURFACE AREA
NUMBER OP
EXTRACTIONS TIME OP EXTRACTIONS
1 >7 DAYS
1 >7 DAYS
METHOD (MATERIAL
CIIACTBREATION
CBNTRB-2) ^
C. SEQUENTIAL CHEMICAL EXTRACTION TESTS
I
TEST METHOD
SEQUENTIAL
EXTRACTION TESTS
LBACHINO FLUID
0.04 M ACETIC ACID
LIQU1D:SOUD RATIO
50:1
MAXIMUM PARTICLE SCB
9.5mm
NUMBER OF
EXTRACTIONS TIMB OF EXTRACTIONS
15
24 HOURS PER
nXTRACTION
-------
TABLE I • EXTRACTION TESTS (continued)
D. CONCENTRATION BUILD-UP TEST
TEST METHOD
SEQUENTIAL
CHEMICAL EXTRACTION
STANDARD LBACII
TEST. PROCEDURE C
(UNIVERSITY OF
WISCONSIN)
LHACH1NO PLUTO
FWB LBACIUNO SOLUTIONS
INCREASING ACIDITY
DI WATER
SYN LANDFILL
LBACHATB
UQUID:5OL1D RATIO
VARIES FROM
16:1 TO 40:1
10:1,5:1
7.3:1
MAXIMUM PARTICLE SIZE
150 um
AS IN ENVIRONMENT
NUMBER OP
EXTRACTIONS
TIME OP EXTRACTIONS
VARIES FROM 2
TO 24 HOURS
J OR 14 DAYS
II. DYNAMIC TESTS (LEACHING FLUID RENEWED)
A. SERIAL BATCH (PARTICLE)
TEST METHOD
MULTIPLE
EXTRACTION
PROCEDURE
0«0)
MWEP
(MONo
EXTRACTION PROCEDURE)
GRADED SERIAL BATCH
(U.S. ARMY)
SEQUENTIAL BATCH
ASTM D479J-88
WASTE RESEARCH
UNIT LBACH TEST
(HARWELL LAB-
ORATORY, UK)
STANDARD LEACHING
TEST: CASCADE TEST
SOSUV, NETHERLANDS
LBACHINO FLUID
SAME AS BPTOX. THEN
WITH SYNTHETIC ACID
RAIN (SULFURIC ACID:
NITRIC ACID IN 00:40%
MIXTURE)
DISntXBD/DBlONEBD
WATER OR OTHER FOR
DISTILLED WATER
TYPE IV REAGENT WATER
ACBTICACID
BUFFERED pll°5
DISTILLED WATER
HNO3 PH 4.0
LIQUID.SOUD RATIO
20:1
10:1 PER
EXTRACTION
SPECIFIC SITE
INCREASES FROM
2:1 TO 96:1
MAXIMUM PARTICLE SEE
9.5mm
9.6 mm OR
MONOLITH
N/A
NUMBER OP
EXTRACTIONS 1
9 (OR MORE)
4
>7
nMEOPBXTRACTlOl
24 HOURS PER
EXTRACTION
II HOURS PER
EXTRACTION
UNTIL STEADY
20:1
IBBDVOL5BLUTIONS
10 BED VOL >6
BLUTIONS
20:1
AS IN ENVIRONMENT
CRUSHING
CRUSHING
10
18 HOURS
2 TO 80 HOURS
2) HOURS
-------
TADI.n 1 • BXTR ACTION TESTS (comtnued)
D. PLOW AROUND TESTS
TBSTMBTHOD
IABADYNAM1CLBACII
TEST (INTERNATIONAL
ATOMIC ENERGY AGENCY)
ISO LEACH TEST
(INTERNATIONAL
STANDARDS OROAN1-
ZATION)
ANS1/ANSI6.I
(AMBRJCAN NATIONAL
STANDARD INSTITUTE/
AMERICAN NUCLEAR
SOCIETY)
DLT
LBACHINO FLUID
DI WATER/SITE WATER
DIWATBR/SITB WATER
DI WATER
DI WATER
C. FLOW THROUGH TESTS
TEST METHOD
STANDARD LBACHINO
TEST: COLUMN TEST
(SOSUV.T/IB
NBTHBRLANDS)
COLUMN ASTM D4IT4-B9
LBACHINO FLUID
DI WATER
HNOjplM
TYPE IV REAGENT WATER
LIQUID;SOUD RATIO
N/A
N/A
N/A
N/A
UQUlDiSOUD RATIO
10:1
ONE VOID VOLUME
MAXIMUM PARTICLE SIZE
ONE PACE PREPARED
SURFACE POLISHING
SURFACE WASHING
SURFACE WASHING
MAXIMUM PARTICLE SIZE
AS IN ENVIRONMENT
AS IN ENVIRONMENT
NUMBEROF
EXTRACTIONS
>I9
>IO
II
18
NUMBER OP
EXTRACTIONS
TIME OP EXTRACTIONS
>6 MONTHS
MOO DAYS
90 DAYS
196 DAYS
TIME OP EXTRACTIONS
10 DAYS
24 HOURS
-------
in.
OTHER TESTS
TEST METHOD
LEACHING FLUID
TADI.E I • HXTRACTION TESTS (conitnutd)
NUMBER OF
LIQU1D:SOLID RAflO MAXIMUM PARTICLE SIZE EXTRACTIONS TIME UP EXTRACTIONS
MCC-5SSOXHLBTTEST DI/SITE WATER 100:1
(MATERIAL CHARACTER-
ISTIC CENTER)
ACID NEUTRALIZATION HMO. SOLUTIONS OF 3:1
CAPACITY INCREASING STRENGTH
CUT AND WASHED
150 urn
0.2MUM1N
I 48 HOURS PER
EXTRACTION
REFERENCES:
I. Compendium of Waste Leading Teals. Waste Water Technology Centre, Environment Canada. Final Draft May 27.19B9
2. Private discussions with OaJI Hansen. Office of Solid Waste, U. S. EPA
-------
PREDICTING THE ENVIRONMENTAL IMPACT OF OILY MATERIALS:
SCIENTIFIC PERSPECTIVE
Larry P. Jackson
INTRODUCTION
This paper is intended to stimulate discussion into new or better ways to evaluate the
potential release of regulated substances from oily wastes. The paper discusses some options
to the currently approved procedures to determine the concentrations of regulated organic
chemicals released into the ground-water regime from improperly managed ofly waste. The
paper also describes a proposed method to evaluate the fraction of an oily waste which is
flowable under the influence of gravity or overburden pressure if the material is improperly
disposed in a landfill The options presented cover, in part, some of the major technical
concerns of the Environmental Engineering Committee of the Environmental Protection
Agency's (EPA) Science Advisory Board (SAB) in their October, 1991 recommendations to the
EPA Administrator1
This paper is prepared from the perspective that accurate, reliable, and cost-effective
analytical procedures can be developed to properly characterize and manage potentially
hazardous ofly wastes. The paper accepts the premise that the regulatory community must
proceed carefully and the "worst case scenario" wfll be considered in any proposed solutions.
The paper seeks to incorporate some of the suggestions of the EPA Science Advisory Board
that methods should take into consideration real world factors such as:
• source matrix properties,
• contaminant properties,
• leachant properties,
• fluid dynamics,
• chemical and physical properties of the waste,
• temporal/spatial dependence,
• measurement methods, and
• physical models.
Presented on July 14,1992 at EPA Woristopff Page 20
on Prcuicbfis ftp cftotroTnootul toxpoct, of Ouy rAtttcrttus "
-------
TECHNICAL ISSUES
Neither the regulatory nor the regulated community has successfully proposed
methods to properly characterize the potential for environmental impact for oily wastes.
Existing leaching tests are known to be technically and mechanically deficient, and no
method exists to measure the amount of flowable, oOy material which may be released from
a waste. Solutions to these problems have not been discussed to any extent in the published
literature nor in the proceedings of symposia and workshops. These issues are recognized as
the major unaddressed problems in evaluating the pollution potential of oily wastes. Any
scenario which proposes to assess the pollution potential of this class of wastes must address
these issues. This section describes the current state of the technology in these areas.
The Oily Waste Extraction Procedure (OWEP, EPA Method 1330A)2 is designed to
evaluate the potential for an oily waste to release metals under aqueous leaching conditions.
OWEP separates the solid material from the oil by solvent extraction. The solid phase is then
leached by Method 1310A, Extraction Procedure Toxkity Test2 and the extracted oil analyzed
directly for the metals of interest The results of the analyses of the two fractions are
combined mathematically. It is generally conceded that this overestimates the leaching
potential of the waste. If the method is applied to the analysis of regulated organic
constituents/ all of the analyte win be deemed 'teachable which is incorrect It should be noted
mat the OWEP has never been suggested as appropriate for organic constituents.
The current approach for analyzing the Iraching potential of solid waste, EPA Method
1311, Toxicity Characteristic Turning Procedure CTCLP)2 differs from the OWEP in that TCLP
attempts to determine the aqueous leachabitHy of the waste for both inorganic and organic
constituents in a single leach test It is very difficult to conduct in a reproducible manner.
Mechanical problems with the test make it time consuming to perform and frequent
reanalysis is required. Precision between replicate tests is very poor. Equipment cleanup is a
major obstacle to laboratory productivity. Costs can run to several thousand dollars per
sample for difficult-to-handle samplgp. The major problems found in conducting the TCLP
are:
• Handling of the sample is messy, effecting weighing of proper amounts into
the extraction vessels. Loss of volatiks occurs.
• Proper sub-sampling of multi-phasic materials is difRmfr. Samples frequently
contain oil, water, and solids. Isolation of solids for extraction is arduous.
• The tumbling action of the two filer extraction vessels forms emulsions making
isolation of the aqueous leachate difficult
• Separation of the leachate from the solid residue after extraction is frequently
impossible because the oily material dogs the filter This is especially serious
when using the zero headspace extractor (ZHE) since the test must be repeated
if mis happens.
Presented on }uh/14,1992 at EPA Workshop H Page 21
on Predu^uig the Eiwuuiuittnlul Iniywi ofOSy Materials"
-------
• Oily wastes frequently yield aqueous leachates and free organic material which
must be separated and analyzed separately/ doubling or tripling the analytical
costs.
• Equipment cleanup is very time consuming, minor amounts of residual organic
material can cany over and contaminate succeeding samples.
These problems are sufficiently severe that both regulators and regulated community
have lost confidence in the utility of the method to estimate the potential environmental
hazard of oily wastes.
PROPOSED APPROACHES
This section discusses four proposed approaches to improving the technical and/or
procedural methods for determining the potential environmental impact of ofly materials.
They are
• Adopt a flowable materials test
• Modify the TCLP.
• Adopt a new method of contacting the leach medium with the waste.
• Devise a new model for determining the amount of a regulated substance
released from an ofly waste by aqngotis leaching mechanisms.
Approach 1 - Flowable Materials Test
The EPA has laid the groundwork for a Flowable Materials Test (FMT) in the 1991
proposed rule making for the Liquid Release Test (LRT), EPA Method 90963. The Agency has
published two reports describing the test for its original application, namely to detect the
release of any free liquid from material destined for land disposal45. The test places a 76mm
diameter by 10mm high sample in a confined chamber under a 50 psi load for ten minutes to
force the release of free liquids.
If the device is modified to provide an tight fitting piston/barrel arrangement
(identical to the design of the zero headspace extractor/ the ZHE) and the indicator paper
holder is replaced with a reinforced screen and fluid collection vessel/ it will be capable of
applying the necessary degree of pressure to the sample necessary to simulate overburden
pressure. The screen will allow for the effective escape and collection of the flowable material
from the solid mass. Both the retained, solids and the collected flowable material can be
analyzed separately using one or more of the suggested experimental changes described in
the following sections.
Presented an Juty 14,1992 at EPA Worktop B Page 22
on 'Predicting the EiaiwiuuaOal Impact of O3y Materials"
-------
Approach 2 • Modify the TCLP
Modification 1 'Addition of Inert Substrate.
One basic problem with the ability to conduct TCLP is the physical nature of oily
material and the impact that has on the conduct of the test as discussed above. The EPA has
addressed this type of problem in Methods 3540 and 35502, Soxhlet Extraction and Sonication
Extraction respectively, where inert adsorbents are added to the waste to provide a free
flowing material with sufficient permeability to allow for efficient extraction. The same
approach can be taken with the TCLP.
The addition of a high surface area, inert matrix like silica beads (or sand) win
effectively immobilize the free phase organic material and provide a free flowing medium for
sample preparation (sub-sampling) and extraction. The increased surface area wffl promote
sohibQization of the organic components into the extraction medium. This approach wrD be
effective for both free liquids and oily solids. If an aqueous phase is also present, adsorption
of the oily material should facilitate separation of the aqueous material prior to extraction.
The presence of the substrate surface as a host site for oily material win minimize the
formation of emulsions during tumbling of the waste/leachant mixture/ provided the
viscosity of the organic material is sufficiently high that the shear forces of the tumbling
action do not separate the liquid material from the solid. After the tumbling sequence, the
solid substrate and absorbed oily material win settle to the bottom of the leaching vessel and
eliminate or minimize the amount of free organic limiij floating at the surface of the
solution, making the nitration step much easier and dogging less likely.
This type-of sorbent bed closely resembles the real world case of oily material spilled
onto or migrating through soil columns until it no longer moves under the force of gravity.
This model of oil coated soil represents the most common real world source of potential
pollutant release from oily wastes.
Modification 2-Use of Fritted Stainless Steel Filter.
Regardless of whether or not the method is modified by the addition of an inert
substrate to immobilize the oily material, the filtration step of the method can be improved.
Agency funded research of improved filtration ™?
-------
Approach 3 - Adopt a New Leaching Technique
The mechanical forces that act on oily waste during tile TCLP tend to separate the oil
from the substrate that was part of the original waste material or the inert material added in
Approach 2. This leads to the formation of emulsions and/or free liquid phases which coat
and dog the filters during the filtration step. Column leaching configurations that are less
physically aggressive than tumbling can be used as the leaching model for oily wastes. The
permeability of the waste material is the key property of the waste which must be controlled
if a column technique is to work (permeability also impacts the efficiency of any extraction
process). Use of inert sorbents, as in Approach 2, can provide the necessary permeability to
allow for uniform flow of the aqueous medium through the waste bed and promote effective
leaching. Uniform flow would be provided by pumping the leachant through the system.
Flow rates can be adjusted to irrinimiTe the shear forces which might dislodge oily
material from the. waste. Flow direction can be changed based on the density of the organic
fluids. Downward flow for materials lighter than water and upward flow for materials
heavier man water wiH minimize the likelihood that oily material win separate from the
substrate during testing. If the fluids do separate/ they will not find their way into the
leachate reservoir without passing through the substrate bed where they win re-deposit on
the surface. Minimum flow volumes per unit mass of -waste wfll become the operational
control of the test rather than the tumbling time that is now used.
The dynamic flow conditions of the column test also allow for efficiencies in
subsequent sample analysis. Modern solid phase sorbents for both organic and inorganic
analytes can be placed between the pump outlet and the head of the column to collect and
pre-concentrate the analytes for future analysis. The use of these sorbents also allows the
introduction of "fresh teacfrant" to the top of the column of waste in a manner snpilar to the
way fresh ground or surface water would contact the waste in the real world scenario. This
would promote maximum release of the target analytes.
The column leach model proposed here resembles the real world case where ground
or surface water percolates through oily material that adheres to the soil, more closely than
does the tumbling action of the TCLP. The column leach approach can be extended to
evaluate the attenuation of sohibilized materials by a representative soil, by placing a soil
layer in the same extraction column as the waste or by passing the tefhate through a second
column placed in series with the waste containing column. This allows for the development
of a modular test sequence in which the same test used to characterize a waste leachate is
used as the source term for attenuation studies, which may be conducted as part of a site-
specific risk assessment This strategy is in keeping with the SAB's recommendation to the
EPA.
Approach 4 - Use a Totally Different Teaching Model
The current TCLP and the two options previously discussed are alternative physical
models of the leaching process. Most problems resulting from these approaches center
around sample handling, leaching, and filtering the leachate. To avoid some of these
Presented on Jiity 14/1992 st EPA Workshop U Aigc 24
on "Predicting tits Eiwiiuiuiinilol Lufiuvl of O3y Matcnus"
-------
problems/ the Agency should consider using well-developed, existing theoretical and
experimental models of the leaching of materials from oily matrices as well and the migration
and interaction of the soluble components with softs. Both the EPA and the American
Petroleum Institute (APD have published significant papers on the approach7*94041. There
is ample experimental evidence that these models are a good first order approximation of the
amounts material actually found from aqueous leaching of oily materials. They apply to both
oily solids and flowable ofly materials. The models depend on the amount of the target
analyte present in the waste, the anarytes physical/chemical properties/ and the chemical
properties of the soil Some of the more important features of these models are discussed
below.
The American Petroleum Institute (APD published a review of historical data relating
fuel composition to the aqueous solubility of its various components7. The review
investigated the relationship between the solubility of the pure hydrocarbon components in
water and the amount found in aqueous solutions mat had been allowed to equilibrate with
fuels (1:10 fuel/water ratio). The study defined the partition coefficient for this process K^
by equation 1:
K -
where Cf = concentration of the component in the fuel, g/L
Cv = concentration of the component in the water/ g/L
This property is related to the solubility of the pure component in water/ S / for a
group of six aromatic compounds by equation 2 which has a correlation coefficient of r7 =
0.99:
Log Kfy =- 0.884 log S + 0.975 (2)
As should be expected/ the relationship between 5 and K&, is a function of the r^ss of
organic compounds being considered (aromatic, aliphatic/ olefinic, etc). When six additional
compounds/ one aromatic/ two olefinic, and three aliphatic/ were considered, the best fit
equation describing the relationship between S and Kf^ became
LogKf,,- - 1.018 log S + 0.706 (3)
and the correlation coefficient/ r2 / dropped to 0.87. Table 1 compares the experimental data
for eleven of the compounds for which data was experimentally determined with the data
derived from equation 3. Most of the data compare favorably with the normal range of
allowable differences between replicate analytical determinations.
Presented on futy 14,1992 at EPA Workshop n Pege25
on rTBnctmg the Emmvniiwiitiil Impact of OSy Mttenais"
-------
TABLE 1
Comparison of Observed and Estimated Hydrocarbon Concentrations
from a Standard Gasoline in Equilibrium with Water (1:10)
HYDROCARBON
Benzene
Toluene
2-Butene
2-Pentene
Ethylbenzene
o-Xylene
m-Xytene
Butane
1 ,2,4-Trimethytbenzene
2-Methytbutane.
Pentane
CONCENTRATION
OBSERVED
58.7
33.4
2.4
2.4
4.3
6.9
11.0
2.7
1.1
3.7
1.0
ESTIMATED
58.8
37.8
32
1.7
3.2
4.7
9.2
5.2
1.8
6.2
22.
This type of model works wen for those cases where the oily waste matrix is the
primary determinate in the partition coefficient in the matrix/ water distribution. The 1984
API report discusses the situation where the amount of oil is very small compared to the
total mass of organic carbon in the soil/sediment/waste matrix and in effect represents oil
absorbed on sod*. Equation 4 applies to these situations.
(4)
where
= soil/water partition coefficient
= the organic carbon partition coefficient
= weight percent organic carbon in the substrate
Presented on July 14,1992 at EPA Worfafeop U
on "Predicting the Eiivuviuuculol Impact of OSy Materials*
Page 26
-------
The organic carbon partition coefficient, K^ , is related to the octanol water partition
coefficient, K^, by equation 5.
Logs:,*. = log Kg, - 0.317 (5)
These models are based on the physical and chemical properties of the target analytes
and the substrates with which they are associated, be it a flowable liquid, solid waste, or sofl.
Accurate and precise methods exist for experimentally determining the input variables to the
models. These variables include but are not limited to:
• analyte concentration in total waste,
• percent organic carbon in soil or waste matrix,
• partition coefficients (fuel/water, soil/water, octanol/water), and
• water solubility of target analytes.
As the data base is expanded, relationships among classes of organic compounds, water,
soils/ and wastes win emerge. These relationships win lead to better empirical and theoretical
understanding of the physical and chemical factors controlling the release of materials to the
environment. New materials can be evaluated without detailed experimental studies by
analogy with similar compounds, wastes, and soils.
Use of this type of approach helps fulfill the SAB's recommendation that more rigorous
scientific procedures be used to determine the potential for release as well as environmental
impact This approach also meets the recommendation mat rugged tests that are less
susceptible to waste matrix effects be used. The approach also uses many of the same
parameters used in determining fate and transport and important measures of environmental
risk; therefore, a more unified model of environmental impact can be developed.
-1
.»•
ROLE OF THE EPA AND PUBLIC &ECTOR GROUPS
The EPA can serve as a catalyst for me necessary research studies for needed to improve
and develop reliable analytical methods. EPA also can leqd in measuring the important
physical and chemical properties, of the analytes, wastes, and soils, that define analyte
behavior in the environment Members of the public sector can contribute laboratory support
and technical expertise to developing the necessary methodology and demonstrating the
applicability and ruggedness of the methods.
These workshops are an ideal expression of how this should work.
Presented m July 14,1992 at EPA Worktop n Page 27
on "Predicting the Environmental Impact of OBy Materials"
-------
1. EPA Science Advisory Board. October, 1991. Leachability Phenomena,
Recommendations and Rationale for Analysis of Contaminant Release by the
Environmental Engineering Committee, Report EPA-SAB-EEC-92-OQ3.
Z EPA, Test Methods for Evaluating Solid Wastes, Physical/Chemical Methods, SW-846,
3rd Edition, Final Update 1, November, 1990
3. * Hazardous Waste Management Containerized Liquids in landfills. October 29,1991.
Federal Register, VoL 56, No. 209, p. 55646.
4 Hoffman, P.A. et aL Development of the Liquid Release Test Research Triangle
Institute Report
5. Background Document for the Liquid Release Test (LRT): Single Laboratory
Evaluation and 1988 Collaborative Study. EPA RCRA Docket # F-91-CLLA-FFFFF.
6. Truesdale, R5. et aL. April 1990. Evaluation and Modification of Method 1311 for
Determining the Release Potential of Difficult-to-Klter Wastes. EPA Contract No. 68-
01-7075, Research Triangle Institute
7. Karickhoff, S.W. and Brown, D5.1979. Determination of Odanol/Water Distribution
Coefficients, Water Solubilities/ and Sediment/Water Partition Coefficients for
Hydrophobic Organic Pollutants, EPA Report EPA-600/4-79-032.
8. Rernbold, KA. et aL 1979-Adsorption of Energy-Rffi^-Organic Pollutants: A
Literature Review. EPA Report EPA-600/3-79-086rC7
9. Hassett, JJ. et aL 1980. Sorption Properties of Sediments and Energy Related
Pollutants, EPA Report EPA/3-80-041.
10. Environmental Research and Technology, Inc. 1984. The Land TreatabOity of
Appendix Vffl Constituents in Petroleum Industry Wastes, API Publication No. 4379.
11. TRC Environmental Consultants, Inc. 1985. Laboratory Study on Solubilities of
Petroleum Hydrocarbons in Groundwater. API Publication No. 4395.
Presented on ftify U, T392 at EPA Workshop E Page 28
on "Predicting the Enoiioninfiitiil Input of OQy MstouZs"
-------
CD
D
Q.
X*
-------
Appendix VI
Office of Solid Waste Methods Section
Memoranda #35, #36
-------
UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
WASHINGTON, D.C. 20460
OFFICE OF
SOLID WASTE AND EMERGENCY RESPONSE
MEMORANDUM i 36
DATE: January 12, 1993
SUBJECT: Notes on RCRA Methods and QA Activities
From: Gail Hansen, Chief >OM j^tf
Methods Section (OS-331)
This memo addresses the following topics:
o 1992 Symposium on Waste Testing and Quality Assurance
o Issue Discussion Groups
o inorganic Methods Workgroup Meeting
o Organic Methods Workgroup Meeting
o QA Workgroup Meeting
o Miscellaneous Methods Workgroup Meeting
o ICP Discussion Group
o HPLC Methods Discussion Group
o SPA Methods Discussion Group
o SFE Methods Discussion Group
o SW-846 Update and TCLP Spike Recovery Correction Removal
Notice Update
o Total Analysis Versus TCLP.
Printed on Recycled Paper
-------
The instrument manufacturers are working with the Agency to
determine the optimum SFE conditions for the major classes of
semivolatile analytes. This input will help expedite development
of a broader scope for Method 3560.
For further information on SFE topics, please contact Barry
Lesnik at (202) 260-7459.
SW-846 and TCLP Spike Recovery Correction Removal Notice
The final SW-846 Update I rule and the proposed Update II rule
packages are both currently at the Office of Management and Budget
(OMB) review step in the regulatory process. It is not known how
long this review step will take. Once the review by OMB is
complete, it is expected that the promulgation of Update I and the
proposal of Update II will take at least 2 months.
The rule to delete the matrix spike correction requirement
from the TCLP which was finalized on June 29, 1990, has been
published (57 PR 55114-56117, November 24, 1992). This rule
withdraws the spike recovery correction requirements from the TCLP
and, except for a few technical and format changes made in the June
29, 1990 rule revising the TCLP, returns the QA provisions of the
TCLP to those promulgated on March 29, 1990 (55 PR 11796).
Specifically, this rule requires the method of standard additions
as the quantitation method for metallic contaminants when
appropriate as specified in the method.
For further information on SW-846 updates or the TCLP rule,
please give Kim Kirkland a call at (202) 260-6722.
Totals Analysis Versus TCLP
Over the past year, the Agency has received a number of
questions concerning the issue of total constituent analysis with
respect to the TCLP. Section 1.2 of the TCLP allows for a
compositional (total) analysis in lieu of the TCLP when the
constituent of concern is absent from the waste, or if present, is
at such a low concentration that the appropriate regulatory level
could not be exceeded. A number of persons have contacted the MICE
Service and have requested clarification on this issue with respect
to a number of waste testing scenarios.
Wastes that contain less than 0.5% dry solids do not require
extraction. The waste, after filtration, is defined as the TCLP
extract. The filtered extract is then analyzed and the resulting
concentrations are compared directly to the appropriate regulatory
concentration.
19
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For wastes that are 100% solid as defined by the TCLP, the
maximum theoretical leachate concentration can be calculated by
dividing the total concentration of the constituent by 20. The
dilution factor of 20 reflects the liquid to solid ratio employed
in the extraction procedure. This value then can be compared to
the appropriate regulatory concentration. If this value is below
the regulatory concentration, the TCLP need not be performed. If
the value is above the regulatory concentration, the waste may then
be subjected to the TCLP to determine its regulatory status.
The same principal applies to wastes that are less than 100%
solid (i.e., wastes that have filterable liquid). In this case
however, both the liquid and solid portion of the waste are
analyzed for total constituency and the results are combined to
determine the maximum leachable concentration of the waste. The
following equation may be used to calculate this value.
[AxB] * [CxD] _
B + [20-1^- x D]
where: A = concentration of the analyte in liquid portion of the
sample (mg/L)
B = Volume of the liquid portion of the sample (L)
C = Concentration of analyte in the solid portion of the
sample (mg/kg)
D = Weight of the solid portion of the sample (kg)
E = Maximum theoretical concentration in leachate (mg/L)
To illustrate this point, the following example is provided:
An analyst wishes to determine if a lead processing sludge
could fail the TC for lead. The sludge is reported to have a low
concentration of lead, and the analyst decides to perform a
compositional analysis of the waste instead of a full TCLP
evaluation. A representative sample of waste is subjected to a
preliminary percent solids determination as described in the TCLP.
The percent solids is found to be 75%. Thus, for each 100 grams of
this waste filtered, 25 grams of liquid and 75 grams of solid are
obtained. It is assumed for the purpose of this calculation that
the density of the filterable liquid is equal to one. The liquid
and solid portion of the sample are then analyzed for total lead.
The following data are generated:
20
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Percent solids = 75%
Concentration of lead in the liquid phase = 0.023 mg/1
Volume of filtered liquid = 0.025 L
Concentration of lead in the solid phase = 85 mg/kg (vet weight)
Weight of the solid phase = 0.075 kg.
The calculated concentration is as follows:
x 0.025L] * [85-^ x 0.075Jcfir]
0.025 L+[20-j=- x 0.075*0-]
In this case, the maximum leachable concentration is below the
5 mg/1 regulatory concentration for lead, and the TCLP need not be
performed.
Non-aqueous based wastes (i.e., oily wastes) may be calculated
in the same manner as described above, except the concentration of
constituents from the liquid portion of the waste (A in the above
formula) are expressed in mg/kg units. Volumes also would be
converted to weight units (kg). The final leachate concentration
is expressed in mg/kg units.
21
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UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
WASHINGTON, D.C. 20460
OFPICE OF
SOLID WASTE AND EMERGENCY RESPONSE
MEMORANDUM / 35
DATE: June 12, 1992
SUBJECT: Notes on RCRA Methods and QA Activities
From: Gail Hansen, Chief
Methods Section (OS-331)
This nemo addresses the following topics:
o 1992 Symposium on Waste Testing and Quality
Assurance
o SW-846 Update
• Final Rule for January 23, 1989 Proposed Rule
- Notice, Proposed Rulemaking for the Second Update to
the Third Edition
o Chlorofluorocarbon 113 (CFC-113) Solvent Replacement
Update
o Environmental Monitoring Methods Index (EMMI)
o Sampling Work Group Formation
o MICE Update
o oily Waste Analysis
o Electronic SW-846 Availability.
3«M*^W —- DfNOH.r*.!**^ J
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Oily Waste Analysis
One of the most frequently asked questions on the MICE
Service concerns the application of the TCLP, Method 1311, to
oily wastes. Many callers request technical guidance on the
extraction of oily wastes due to the difficulty in the filtration
on these types of waste. In many cases, an oily waste does not
filter completely due to premature clogging of the glass fiber
filter. This can result in the retention of standing liquid on
the glass fiber filter. Material that do not pass through the
glass fiber filter at the conclusion of the filtration step is
defined by the method as the solid phase of the waste. The solid
phase is then subjected to the leaching procedure of the TCLP.
For oily wastes, clogging of the glass fiber filter can result in
an overestimation of the amount of solid material available for
leaching.
To solve this problem, the Agency recommends a conservative
approach, one that probably will overestimate the amount of
leaching. Rather than performing the TCLP extraction on the
unfiltered portion of the oily waste, assume the waste is 100%
liquid (e.g., will pass through the glass fiber filter) and
perform a totals analysis on the oily waste to determine if the
oil exceeds the appropriate regulatory level.
Filterable waste oil generated during the TCLP must be
analyzed for a variety of organic and inorganic analytes. The
OSW recognizes the difficulty in achieving acceptable performance
for the analysis of waste oil using methods currently provided in
SW-846. As a result, the Agency will provide several new methods
for the preparation and analysis of oil samples to the Organic
Methods Workgroup in July. In addition; a microwave assisted
digestion procedure should improve the analysis of metals and
will be proposed as part of the Second Update of the Third
Edition of SW-846. Brief descriptions of these techniques are
provided below, for additional information on the organic
procedures contact Barry Lesnik at (202) 260*7459. For
additional information on microwave digestion contact Ollie
Fordham (202) 260-4778.
The use of purge-and-trap (Method 5030) for volatiles in oil
generally results in severe contamination of analytical
instrumentation. Traps, transfer lines and chromatography
columns may become contaminated with oil. This leads to elevated
baselines, hydrocarbon background in subsequent analyses, and
cross-contamination. Headspace (Method 3810) is currently
allowed only as a screening procedure in SW-846. The Agency is
evaluating the use of headspace in conjunction with isotope
dilution mass spectrometry for the quantitative analysis of
volatiles in oil. Headspace reduces interference problems
encountered with purge-and-trap. However, headspace quantitation
can be questionable because the distribution of analytes is not
10
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the same in different types of samples. That difficulty appears
to be minimized by the use of isotope dilution calculations.
Headspace/isotope dilution analysis will require the promulgation
of two new SW-846 methods: Method 5022, Volatiles by Automated
Headspace, and Method 8266, Volatiles by Isotope Dilution GC/MS.
Performance data for the analysis of motor oil vill be presented
to the Organics Workgroup and during a platform talk at the July
Symposium. Draft methods should be available for limited
distribution by September.
Headspace/isotope dilution will require that laboratories
acquire hardware and provide additional analyst training.
Therefore, an alternate Solvent Dilution Direct Injection (Method
3585) option for Method 8260 is also being evaluated. While use
of the direct injection technique vill result in more instrument
contamination, it may be appropriate for laboratories that
analyze only a limited number of oil samples. Method performance
data will also be presented for direct injection during the
symposium in July.
The analysis of semi-volatile target analytes is also
difficult with present methods. While gel permeation cleanup
(6PC) is effective, it can only be used for small oil samples
(<0.5 g). Work is in progress to evaluate partition and
extraction cleanup procedures for waste oil. Partitioning oil
between dimethyl formamide (DMF) and hexane or extraction of oil
with methanol/DMF followed by acid/base partitioning has proved
successful prior to the analysis of chlorophenols in waste oil.
A similar approach is being evaluated for the analysis of
organochlorine pesticides. Work to date has demonstrated that
steam distillation and vapor/vapor extraction procedures are not
appropriate for petroleum products.
The Agency will propose a new digestion procedure (Method
3051) for inorganic samples in the Second Update of the Third
Edition of SW-846. The procedure uses a microwave oven to heat
the acid during digestion of sediment, sludge, soil and oil
samples. The resulting digestate can be analyzed using atomic
absorption (AA) or inductively coupled plasma (ICP) methods in
SW-846. Microwave assisted digestion is suitable for all oils
including oils that contain particulates. The only current
inorganic preparation method suitable for oils is Method 3040, a
dissolution procedure. In contrast to Method 3051, Method 3040
is suitable only for metals dissolved in oil. Method 3040 can be
used to show that an oil is hazardous based on the concentrations
of dissolved metals.
Electronic SW-846
SW-846 now can be purchased from private vendors in an
electronic format. A brief description of each known package and
information on how to obtain copies of each are given below.
11
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The SW-846 Authority is published in electronic format by
Virtual Media Corporation. The SW-846 Authority is an
comprehensive electronic publication designed to track and manage
regulatory issues. By using IQTP (Intelligent Query Text
Processor), the SW-846 Authority utilizes a comprehensive index,
allowing users full text and retrieval capabilities. Users have
access to thousands of EPA generated regulatory documents and
official notices, including the full text of Federal Register
Preambles. Other features of the SW-846 Authority include:
• RCRA Act (SWDA)
• RCRA 40 CFR Parts 260-265, 270-272
• SW-846 Solid Waste Test Methods Manual
• RCRA Inspection Manual.
For information on the SW-846 Authority call (800) 645-4130
or write to:
Virtual Media Corporation
14455 North Handen Road, Suite 201
Scottsdale, AZ 85260
Electronic E.P.A. Methods** 1.1 is offered by Chemsoft*"
Corporation as an electronic database of all EPA methods. This
program is designed for rapid search and retrieval of EPA methods
by method number, analyte, title, type of instrumentation, or CAS
number. Each program contains the full text of the methods as
they appear in the appropriate EPA manual. Use of this software
requires Windows 3.0. The following programs are available
either separately or may be purchased as a single package:
• EPA SW-846 Series Methods
• EPA 500 Series Methods
• EPA 600 Series Methods
• EPA Water and Waste Methods.
For further information on Electronic E.P.A. Methods, call
(800) 536-0404 or (707) 864-0845 or write to:
WindowChem Software, Inc.
1955 West Texas Street, Suite 7-288
Fairfield, CA 94533-4462
The Methods Section will provide additional information in
future memoranda on other sources of electronic SW-846 media when
we become aware of them.
12
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Appendix VII
Recommendations and Rationale for Analysis of
Contaminant Release by the Environmental Engineering
Committee
Science Advisory Board
October 1991
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United States Science Advisory Board EPA-SAB-EEC-92-003
Environmental Protection (A-101F) October 1991
Agency
VEPA Leachability
Phenomena
Recommendations and
Rationale for Analysis of
Contaminant Release by the
Environmental Engineering
Committee
Printed on Recycled Paper
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UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
WASHINGTON, O.C. 20460
EPA-SAB-EEC-92-003
OFFICE OF
_ . . -_ ,__. THEADMWBTRATOR
October 29, 1991
Honorable William K. Reilly
Administrator
U.S. Environmental Protection Agency
401 M Street, 8.W.
Washington, D.c. 20460
Subject: Leachability: Recommendations and Rationale
for Analysis of Contaminant Release
Dear Mr. Reilly:
The Leachability Subcommittee (L6) of the Science Advisory
Board's Environmental Engineering Committee (EEC) has prepared
the attached recommendations and rationale on leachability, an
important release term related to solid wastes and contaminated
soils, for your consideration.
Over the past decade, the EEC has reviewed a number of EPA
issues involving leachability phenomena and noted several
problems relating to this release term that were common to a
variety of EPA offices. The Committee believed that these common
problems would be best called to the Agency's attention through a
general review of leachability phenomena.
Drafts of this report on leachability have been reviewed at
a series of Subcommittee, Committee, and Executive Committee
meetings over the past 18 months. This included both a session
on February 26, 1990, devoted to assessing the Agency's varied
needs on leachability-related information, and a Technical
Workshop on May 9, 1990. The workshop assisted in determining
how leacnability phenomena should be used to determine how a
waste will leach when present under various scenarios in the
environment.
The following recommendations have been developed. First,
in regard to leachability test development we recommend:
a) incorporation of research on processes affecting
leachability into EPA's core research program to better define
and understand principal controlling mechanisms,
b) development of a variety of contaminant release tests,
rather than focusing on mimicking a single scenario,
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e) development of improved release and transport-
transformation models of the waste matrix to complement the
leaching tests, and
d) field validation of the tests and models/ and
establishment of release-test accuracy and precision before tests
are broadly applied.
Hext, in regard to the application of such tests and models,
we recommend:
e) use of a variety of contaminant release tests and test
conditions which incorporate adequate understanding of the
important parameters that affect leaching in order to assess the
potential release of contaminants from sources of concern. A
medical analogy is that no physician would diagnose on the basis
of one test showing only one aspect of the problem,
f) development of a consistent, easily applied, physical,
hydrologic, and geochemical representation for the phenomenon or
waste management scenario of concern,
g) identification and application of appropriate
environmental conditions for tests in order to evaluate long-term
contaminant release potential as required under varying statutes,
and
h) coordination between the Agency's programs which develop
leachability tests with those that develop the environmental
models in which the release terms are used.
Finally, we recommend:
i) establishment by the Agency of an inter-office, inter-
disciplinary task group, including ORD to help implement these
recommendations, and
j) development of an Agency-wide protocol for evaluating
release scenarios, tests, procedures, and their applications.
These recommendations are made with the anticipation that an
improved understanding of the fundamental scientific principles
that control contaminant release and transport within a waste
matrix will allow better regulatory and technical decisions to be
-------
nade in eases where the potential exists for leaching of
contaminants into the environment.
We are pleased to be of service to the Agency, and hope that
you vill find this effort useful, we look forward to your
response to the recommendations cited above.
Dr. Raymond C. Loehr, Chairman Mr. Richard A. Conway, Cl
Executive Committee Environ. Engineering Committee
Dr. C. H. Ward, Chairman
Leachability Subcommittee
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ABSTRACT
The Leacbability Subcommittee (LS) of the Environmental
Engineering Committee (EEC) of the EPA Science Advisory Board
(SAB) conducted a self-initiated study and prepared a report on
the topic of leachability phenomena. The intent of this report
is to provide recommendations and rationale for analysis of
contaminant release to the staff in the various offices of the
Environmental Protection Agency (EPA). The nine recommendations
from the report are highlighted as follows:
1) A variety of contaminant release tests and test condi-
tions which incorporate adequate understanding of the important
parameters that affect leaching should be developed and used to
assess the potential release of contaminants from sources of
concern.
2) Prior to developing or applying any leaching tests or
models, the controlling mechanisms must be defined and
understood.
3) A consistent, replicable and easily applied, physical,
hydrologie, and geochemieal representation should be developed
for the vaste management scenario of concern.
4) Leach test conditions (stresses) appropriate to the
situations being evaluated should be used for assessing long-term
contaminant release potential.
5) Laboratory leach tests should be field-validated, and
release test accuracy and precision established before tests are
broadly applied.
6) More and improved leach models should be developed and
used to complement laboratory tests.
7) To facilitate the evaluation of risk: implications of
environmental releases, the Agency should coordinate the
development of leach tests and the development of models in vhich
the release terms are used.
8) The Agency should establish an inter-office, inter-
disciplinary task group, including ORD to help implement these
recommendations and devise an Agency-vide protocol for evaluating
release scenarios, tests, procedures, and their applications.
9) Core research on contaminant release and transport within
the vaste matrix is needed.
Key Words; leachability, leachability phenomena, leach tests and
methods, leaching chemistry, leaching models
ii
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Z. EXECUTIVE SUMMARY
In vaste management, including managing the effects of
spills or other releases which are sources of underground
contamination/ a critical issue is the assessment of the
potential for constituents to leach to the environment. The
Environmental Engineering Committee (EEC) of the Science Advisory
Board (SAB) undertook a study of this issue because it noted
several common problems relating to this release term as it
reviewed/ over the past decade/ various leaching tests and risk
models for several EPA offices. Tests such as the Extraction
Procedure (EP) and the Toxicity Characteristic Leaching Procedure
(TCLP) had, and continue to have, scientific limitations, yet
were being inappropriately and in some cases widely used. Often
tests were developed without rigorous review. A self-initiated
study seemed appropriate to define the leachability problem
better and to offer advice on its resolution.
The EEC established a Leachability Subcommittee (L8) that
addressed:
1) Needs of the Agency and regulated communities to
quantify leachability (releases) of contaminants to the
environment.
2) State-of-the-art and science related to fundamental
principles and practice in predicting leaching of constituents
from wastes, contaminated soils, and other sources.
3) Recommendations to improve the scientific understanding
and application of leaching tests.
Workshops were held, literature was analyzed, and
findings were discussed over an 18-month period leading to the
preparation of this report.
The various needs for tests and models to predict leaching
are defined. Tests developed and used in the U.S. and Canada are
summarized. The scientific considerations important in design
and interpretation of leachability tests are presented. This
information, expert advice and analysis by workshop participants,
and reviews by SAB members, resulted in guidance which should, if
progressively implemented, significantly strengthen the Agency's
ability to assess appropriately leaching of contaminants from
hazardous wastes, contaminated soils and other sources.
This guidance, in the form of nine recommendations, is
summarized as follows:
1) A variety of contaminant release tests and test
conditions which incorporate adequate understanding of the
important parameters that affect leaching should be developed
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and used to assess the potential release of contaminants from
sources of concern.
2) Prior to developing or applying any leaching testa or
models, the controlling mechanisms must be defined and
understood.
3) A consistent/ replicable and easily applied, physical,
hydrologic, and geoehemieal representation should be developed
for the waste management scenario of concern.
4) Leach test conditions (stresses) appropriate to the
situations being evaluated should be used for assessing long-term
contaminant release potential.
5) Laboratory leach tests should be field-validated, and
release test accuracy and precision established before tests are
broadly applied.
6) More and improved leach models should be developed and
used to complement laboratory tests.
7) To facilitate the evaluation of risk implications of
environmental releases, the Agency should coordinate the
development of leach tests and the development of models in which
the release terms are used.
8) The Agency should establish an inter-office, inter-
disciplinary task group, including OXU), to help implement these
recommendations and devise an Agency-vide protocol for evaluating
release scenarios, tests, procedures, and their applications.
The task group should also be charged with recommending vhat the
appropriate focal point (s), responsibilities, and organisational,
budgetary and communication links should be within the Agency for
the most effective, continued and ongoing support and pursuit of
the research, development and utilisation of methods and
procedures.
9) Core research on contaminant release and transport within
the waste matrix is needed.
ZZ. INTRODUCTION
Zn both hazardous and non-hazardous waste management, one of
the most critical issues is the assessment of the potential for
constituents contained in the source material to leach or
otherwise be released to the environment. Approaches to estimate
potential release of organic and inorganic constituents and their
subsequent environmental migration and associated health risks
are important in many situations (e.g., pollution prevention,
risk reduction, restoration-remediation and hazard identi-
fication) .
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Appendix VIII
USEPA Region II
Special Analytical Services Request
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SAS Number
U.S. ENVIRONMENTAL PROTECTION AGENCY
CLP Sample Management Office
P.O. Box 818 - Alexandria, Virginia 22313
Phone: (703) 557-2490 - (FTS) 557-2490
SPECIAL ANALYTICAL SERVICES
Client Request
I 1 Regional Transmittal ' ' Telephone Request
A. EPA Region/Client:
B. RSCC Representatives:.
C. Telephone Number: ( )
D. Date of Request:
E. Site Name:
Please provide below description of your recent request for
Special Analytical Services under the Contract Laboratory
Program. In order to most efficiently obtain laboratory
capability for your request, please address the following
considerations, if applicable. Incomplete or erroneous
information may result in a delay in the processing of your
request. Please continue response on additional sheets, or
attach supplementary information as needed.
l. General Description of Analytical Service Requested:
Analysis of soil samples by TCLP for TC analytes.
Analysis of aqueous blanks for TC analytes.
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2. Definition and number of work units involved (specify
whether whole samples or fractions; whether organics or
inorganics; whether aqueous or soil and sediments; and
whether low, medium, .or high concentration):
Number of Samples Matrix Concentration Analysis
3 Soil Low TCL(plus
pyridene
and m-
cresol),
TAL,
2,4-D and
2,4,5-TP
by TCLP
Water Low TCL (plus
Field pyridene
Blank' and m-
cresol),
TAL,
2,4-D and
2,4,5-TP
3. Purpose of analysis (specify whether Superfund (Enforcement
or Remedial Action), RCRA, NPDES, etc.):
4. Estimated date(s) of collection:
5. Estimated date(s) and method of shipment:
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6. Number of days analysis and data required after laboratory
receipt of samples:
Environmental samples must undergo TCLP extraction within
the following time periods after sample receipt:
Mercury 2 6 days
Other Metals 178 days
Volatiles 12 days
Pest/Herb/BNA 12 days (7 additional days
from TCLP extraction to
preparative extraction)
Environmental TCLP sample extracts must be analyzed within
the following time periods after extraction:
Mercury 2 8 days
Other Metals 180 days
Volatiles 14 days
Pest/Herb/BNA 40 days
Field and trip blanks must be analyzed within the following
time periods after sample receipt:
Mercury 26 days
Other Metals 6 months
Volatiles 10 days
Pest/Herb/BNA 5 days to extraction,
40 days to analysis
The complete data package containing all the sample delivery
groups (SDG) associated with this case must be submitted as
one data package in its entirety within 35 days from the
verified time of receipt of the last sample in this case.
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7. Analytical protocol required (attach copy if other than a
protocol currently used in this program) :
Parameter
TCLP Metals
TCLP VOAs
TCLP BNAs
TCLP Pest
TCLP Herb
Metals
VOAs
BNAs
Pest
Herb
Matrix
soil
soil
soil
soil
soil
water
water
water
water
water
Preparation
SW-846
SW-846
SW-846
SW-846
SW-846
1311
1311
1311
1311
1311
Analysis
CLP ILM03.0
CLP OLM01.8
CLP OLM01.8
CLP OLM01.8
SW-846 8150A
CLP ILM03.0
CLP OLM01.8
CLP OLM01.8
CLP OLMO1.8
SW-846 8150A
Only the 39 TC analytes shall be reported.
Revision 1 of Method 8150A, dated November 1990, shall be used to
analyze herbicides.
The July 1992 version of Method 1311 shall be used.
8. Special technical instructions (if outside protocol
requirements, specify compound names, CAS numbers, detection
limits, etc.):
All Fractions
If dilutions are necessary due to an analyte being out of
calibration range, they must be done in increments of 10.
The raw data of all the dilutions must be provided; the
final result of the analyte shall be calculated from the
least dilution that would bring the analyte concentration
within the calibration range.
A TCLP blank must be carried through the extraction,
digestion, and analytical procedures.
The maximum number of samples in a sample delivery group
(SDG) is 20.
Field blanks and trip blanks do not require MS/MSB. The
matrix spike shall be added to the TCLP extract, not the
environmental sample.
Metals
The CRDLs for the TC metals shall be twenty times the CRDL
in the current SOW, except for mercury, which will
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be two hundred times higher. The matrix spike analytes will
be spiked at five times the contract specified
concentrations. The TCLP Section 8.4 criteria for method of
standard additions shall be followed.
Organics
Volatile and semi volatile TCL fractions will be diluted
five times before analysis, which will increase the CRQLs by
a factor of five. Pesticides will be diluted ten times
before analysis, which will increase the CRQLs by a factor
of ten. The TCL surrogates will be spiked at five times the
contract specified concentrations. The TCL matrix spike
analytes shall consist of all the TC analytes except
toxaphene, and shall be spiked at ten times the contract
specified concentrations.
When analyzing BNA samples, the 2/88 CLP extraction
procedure must be used. Initial and continuing
calibrations are required for pyridine and m-cresol.
There are no calibration acceptance criteria for pyridine or
m-cresol.
Herbicides
Follow requirements in 8150A and 8000A.
Analytical results required (if known, specify format for data
sheets, QA/QC reports. Chain of Custody Documentation, etc). If
not completed, format of results will be left to program
discretion.
The following TCLP deliverables shall be supplied:
1. The TCLP and preparative extraction dates and analyses
dates. Data to justify selection of TCLP extraction
fluid.
2. A physical description of the samples.
3. The sample weights and the extraction fluids weights.
4. The final volume of TCLP extract and the volume of
extract analyzed.
5. The calculations used to compute percent dry solids and
the weight of the liquid phase (if applicable).
6. Extraction logs for each sample, indicating the volume
and pH of acid added. Were inorganic sample extracts
properly preserved?
7. A description of the materials of construction for
extraction vessels, filtration devices, and ZHE
extraction devices (i.e. glass, Teflon, PVC, stainless
steel etc.).
8. The calculations used to compute TCLP extract
concentrations for multiphasic samples.
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9. When VOA samples consist of oily waste that cannot be
filtered, describe how the TCLP extract is separated
from the oily waste.
10. A copy of the sampling log.
11. Any evidence of leakage in the ZHE device.
TCLP Worksheets 1, 2, 3, and 4 (attached), must be
submitted with the analytical data.
A TCLP bank must be analyzed in addition to method
blanks.
The following analytical results shall be submitted for
Method 8150 A analysis:
The laboratory must submit all documentation including: SAS
packing lists, traffic reports, chain of custody forms, and
sample preparation information. Analytical and QC results
shall be submitted on the following modified CLP/SOW
pesticide forms: Form I (Analytical Results), Form II
(Surrogates), Form III (Matrix Spikes), Form IV (Method
Blank), Form VI (Initial Calibration), Form VII (Calibration
Verification), Form VIII (Analytical Sequence) and Form X
(Identification Summary). All QA/QC information, including
laboratory generated standards and sample chromatograms,
must be submitted. A written narrative describing problems
encountered in receipt or during analysis and corrective
actions taken (including telephone logs, etc.) must be
provided. All documents (modified CLP forms, raw data,
etc.) related to re-extraction/re-analysis must also be
submitted in its entirety.
10. Other (Use additional sheets or attach supplementary
information, as needed):
The following requirements apply to method 8150A:
The laboratory must supply any information required to
reproduce, during independent data review, all results
reported by the laboratory. The laboratory must supply a
detailed example calculation that clearly demonstrates the
manner in which the initial and final results were derived.
Where applicable, each component of the calculation must be
explained (e.g., if the calculation include a dilution
factor, it must be specified how each dilution occurred).
-------
11. Name of sampling/shipping contact:
12.
Phone:
Data Requirements
For VOAs, BNAs, pesticides and metals, follow CLP criteria.
The following requirements apply to 815OA herbicide
analysis:
Parameter
2,4-D
2,4,5-TP
Detection Limit
As per method
8150A
Precision Desired
As per method
8150A
Estimated Quantitation Limits (EQL) can be computed from
Table 1 & 2 of method 8150A for various parameters.
13. QC Requirements
For VOAs, BNAs, pesticides, and metals, follow CLP criteria.
The following requirements apply to 8150A herbicide
analysis:
Audits Required
Initial Calibra-
tion
Continuing(mid-
level std) Cal-
ibration
Surrogate
Method Blank
Duplicate
Matrix Spike
Frequency of Audits
See Method 8000A
Every 10 samples
All samples, etc.
1 per 20 samples
1 per 20 samples
l per 20 samples
Limits
(% or Concentration)
%D
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8
Audits Required Frequency of Audits (% or Concentration)
For VOAs, BNAs, pesticides, and metals, follow CLP criteria.
For 8150A and TCLP, follow method criteria.
14. Action Required if Limits are Exceeded
For VOAs, BNAs. pesticides, and metals, follow CLP protocol
For 8150A, reextract and reanalyze.
Please return this request to the Sample Management Office as
soon as possible to expedite processing of your request for
special analytical services. Should you have any questions, or
need any assistance, please contact your Regional representative
at the Sample Management Office.
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TCLP Worksheet No. 1
Sample Description
Laboratory Sample No.
Field Sample Mo.
&. Sample Hesetiglsa) ' ' " " -, ;
Number of phases
1. solid
2. liquid
a. lighter than water
b. water
c. heavier than water
BL PercefrtSoKaftese - ' •• ,
1. weight of filter
2. weight of subsample
3. weight of filtrate
4. weight percent solids (wet)1
5. weight percent solids (dry)2
6 volume of initial aqueous filtrate
7. volume of initial organic filtrate
•
1. The weight percent wet solids is given by the equation:
weight of subsample - weight of filtrate
weight of subsample
2. The weight percent dry solids is given by the equation:
(weight of dry waste * filter) - weight of fitter
weight of subsample
10Q
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10
Discussion and Recommendations
TCLP Worksheet No. 1
Sample Description
This worksheet documents important information regarding the general description of the sample and the number of
phases observed in the sample as received from the field. This information is used to determine the amount of leaching
fluid used to leach solid materials and the weighting factors used when calculating final analyte concentrations from
multi-phasic samples.
A. Sample Description
Number of phases -• The number of phases present in the sample determine how the TCLP is conducted. Solid
materials having no visible liquid phase are extracted as received from the field and the analyte concentration
found in the leachate is the reported value. Liquid materials having no measurable solids content ( < 0.5 wt. %
dry solids) are defined as the TCLP extract (5 2.1) and are filtered and analyzed directly.
Multi-phase samples must be separated ( f 7.1.1.2) and each phase treated individually. Aqueous phases may be
combined with the leachate from solid phase materials before analysis if the two aqueous materials are compatible
( H 7.2.13.2). If the two aqueous materials are not compatible, than each liquid must be analyzed by the
appropriate methods and the results combined numerically to determine the final reported value ( f7.2.14).
A.1. Solid - record the visible presence of a solid material heavier than water. If the sample contains more than
one solid phase ( example, wood chips and sediment mixed with water) record the information in the
laboratory notebook.
A.2. Liquid - record the number of liquid phases observed in the sample according to their apparent density. It
may be impossible to distinguish apparent density if only one liquid phase is observed and there is no
indication on the accompanying chain-of-custody form (COC). rf this is the case, record it as aqueous material
and let the subsequent analytical record show if the liquid is organic after the container is opened at the
appropriate time.
B. Percent of Solid / Liquid Phase(s) - paragraphs 7.1.1 through 7.1.2.3 of the method describe the procedure to
follow for the determination of the percent solids of the samples. It is also convenient to measure the percent of
any non-miscible liquid phases at this point because the information is required in ^ 72.14.
Laboratory subsampling of the material delivered to the laboratory must be thoroughly documented. The total
contents of the sample container should be considered as "the sample" and care must be taken to ensure the
representativeness of any subsample. Heterogeneous and multi-phasic materials can be difficult to subsample
properly and frequently require significant judgment on the part of the analyst.
Discussion ~ At this point, it is important to review the COC and confirm the number of containers of each
sample provided to the laboratory and the types of analyses requested. If the analysis of volatile components is
requested, the determination of percent solids in mufti-phasic samples must be completed before proceeding to the
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11
leaching of the solid material in the zero headspace extractor (ZHE) to prevent overfilling the ZHE. It isrbest if a
separate sample has been provided for this purpose ft 63). The laboratory should establish an SOP to address
how to proceed if only one container is available.
It is common that when more than one container of multi-phasic materials is received from the field, each
container will show different amounts of each phase. This provides a challenge to the laboratory which must
report the data based on percent phase composition of the sample. A practical solution is to record the depth
(measured from outside the container) of the layers in the each container after the contents have been allowed to
settle and determine the combined volume of each phase in all the containers. Then measure the phase
composition on a single container (after thorough mixing to obtain a representative subsample). Combine these two
sets of values to determine the correct volume/mass adjustments on the TCLP results.
The laboratory should also estabRsh an SOP on how to proceed when only a limited amount of sample is available
and the analyses requested exceed the amount of sample provided.
B.I. Weight of filter - This value must be measured before loading the filter into the filter holder because the
mass of the filter is used in performing the calculation for percent dry solids.
B.2 Weight of sample aliquote •• a representative 100 gram sample (f 7.1.1.5) is withdrawn from the sample
container for filtration. If liquid material is decanted from the sample before subsampling, its volume/weight must
be recorded and factored into the calculations of percent solids.
Discussion •• Many multi-phasic samples are difficurt to fitter. This is especially true of oily wastes and
sludges. The method directs that any material retained by the filter after following the instructions is defined
as sofftf waste ft 7. J. 18). Experience has shown that the reproducMrty of the percent solids determination
with these types of samples is highly variable. Subsequent steps in the extraction procedure ft 7.2.5 and
7.3.4.2) use the % solids value to estimate the mass of the original waste used to obtain an appropriate
sized subsample of the solid for extraction.
The method directs that the material retained by the filter be dried at 100 ± 20 °C ft 7.1.23) to
determine the percent dry solids. This may not be achievable for organic murti-phasic materials because of
safety considerations and the fact thai many organic liquids boil considerably higher than water and it may
be impossible to achieve a constant weight for successive weighings (± 1%).
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12
The laboratory should establish a standard operating procedure (SOP) addressing these types of samples.
Basically, the laboratory has three choices of how to proceed. It may
• attempt to dry all samples as directed by the method;
• dry samples containing bhty water:as the liquid phase; and/or
. • define the retained'material as a dry solid for the purpose of further testing.
This decision may have signfficant impact on the amowt of material selected for leach testing and on the
reported anah/te values. The laboratory'"s/ioiibf,considerdiscussing this issue with their clients and any
regulatory groups to whom the data will be submitted.
B. 3 Record weight of filtrate.
B. 4 Weight percent solids(wet) equals:
weight of subsample - weight of filtrate v- 10Q
weight of subsaonple
The procedure defines the material retained by the filter as the solid phase of the waste (t 7.1.1.8). This
value is used to calculate the volume of the original multi-phasic material which must be filtered to yield the
proper amount of solid waste for the extraction iprocedure.-
B.5 Weight, percent solids (dry) -^the total mass, of the filtered solids and the filter are removed from the filtration
apparatus and dried at 100 ± 20 °C until-a constant weight is achieved (f 7.122). This value is used to
calculate the'dry solids content of the waste. Use caution when drying samples that may contain flammable
material. It is important to factor in the tare weight of the filter for samples that have low solids values.
The weight percent solids (dry) is calculated by the equation:
(weight of dry waste + fitter) - weight of filter
weightofsubisample
If the weight percent dry solids is > 0.5%, the total waste is defined as a solid waste and steps must be
taken to collect the appropriate weight of solid material for extraction (f 7.1.2.4).
B.6 Volume of initial aqueous filtrate - this value is used in 1 72.14 and 7.3.14 in the final calculation of analyte
concentration.
B.7 Volume of initial organic filtrate - this value is used in f 7.2.14 and 7.3.14 in the final calculation of analyte
concentration:
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13
TCLP Worksheet No. 2
Selection of Extraction Fluid
Laboratory Sample No.
Held Sample No.
C. Ixtrai^oa FltiiOefei?i*iB3^n -• doesj^ - '
1. particle size reduction? yes/no
2. sample weight, / if 5.0 ± 0.1 grams
3. volume of water, / if 96.5 ± 1.0 ml added
4. initial pH (after 5 min. mixing time)
5. if pH > 5.0, ^ if 3.5 mL 1N HCI added
6. / if heated and held at 50 °C for ten
minutes
7. secondary pH (at room temp.)
D~ Setecfien af Sclraetisa $M * - * " * < - , - , w , -
1. S rf pH from C.4 or C.7 is < 5.0, use
extraction fluid No. 1.
2. / rf pH from C.7 is > 5.0, use extraction
fluid No. 2
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14
Discussion and Recommendations
TCLP Worksheet No. 2
Selection of Extraction Fluid
for
Metals, Semi-volatile Organic Components, and Pesticides/Herbicides
This worksheet documents the important steps which should be followed to correctly
determine the appropriate extraction fluid for leaching solid wastes for the analysis of
metals, semi-volatile organic components, and pesticides/herbicides. This procedure does
not apply to the determination of volatiles using the zero headspace extractor (ZHE).
Discussion -- the Environmental Protection Agency's "worst case" waste disposal model
assumes mismanaged wastes will be co-disposed with municipal solid waste in a 5:95
ratio. These wastes will be exposed to /caching by the acidic fluids formed in municipal
landfills. The EPA's model further assumes the acid/base characteristics of the waste will
be dominated by the landfill fluids. The TCLP laboratory procedure directs that alkaline
wastes be extracted with a stronger acidic leach fluid than acid or neutral wastes so that
the alkaline nature of the waste will not control the leaching chemistry of the TCLP test.
This is in keeping with the waste disposal model's assumption that the acid fluids in the
landfill will dominate leaching chemistry over time.
The procedure described in ^ 7.1.4 of the method addresses the determination of the
appropriate extraction fluid. It is a short term test whose results can have a significant
impact on the final analytical results if the wrong extraction fluid is selected. This is
especially true for metals determinations because of their sensitivity to the pH of the leach
medium. The following discussion examines each step of the procedure and points out
some sensitive technical points and how they can affect the results.
\ 7.1.4.1 Particle size of test material — The requirement to use 1mm particle size material
in the test recognizes the fact that in a short term reaction between a liquid and a solid,
high surface area is the most important characteristic of the solid. The rate of the reaction
is controlled by the rate of diffusion of the liquid into the pores of the solid so a high
surface area is necessary if the results of a short term test are to be reliable. Therefore,
failure to take a representative subsample of the solid material and perform the necessary
particle size reduction can result in significant bias. This is especially true rf the waste
contains a wide range of particle sizes and only the fines are selected for testing.
f 7.1.4.3 Heating of the reaction mixture — The method specifies that the waste/acid
slurry is to be held at 50°C for ten (10) minutes. Care should be taken to heat the sample
to 50 °C as rapidly as possible without overheating. When the sample has completed the
ten minute period at temperature, it should be allowed to cool and the pH determined as
soon as possible. The longer the reaction between the acid solution and the solid waste is
allowed to continue, the more likely that a falsely high pH reading will result. This will
result in improper selection of the more acidic extraction fluid. Failure to reach and hold
the required temperature can result in an artificially low pH reading for the test solution,
leading the incorrect selection of the less acidic extraction fluid.
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15
C. Extraction Fluid Determination (^ 7.1.4)
C.1. Indicate if particle size reduction is required for the sample.
Discussion - the laboratory should consider establishing an SOP to address the
particle size reduction requirements for the TCLP procedure. Most solid samples will
not be received from the field with a particle size of 1mm as required for this step
of the procedure (\ 7.1.4.1). Many multi-phasic samples will not be amenable to
size reduction because of the nature of the sample. Samples containing pebbles,
rocks, or debris may be difficult to size reduce if the larger particles are hard. Proper
subsampling of the waste may be difficult if the waste is heterogeneous.
C.2. Sample weight - check the box if 5.0g of sample is used in the test. Record the
actual weight if a different sized sample is used.
C.3. Volume of water - the volume of water used in the test is dependant on the weight
of sample being tested. If the sample weight (above) is 5g and 96.5 mL of water is
added, check the box. If the weight is not 5g, record the volume of water added.
( # of grams X 19.3mL).
C.4. Initial pH - record the pH of the slurry after a five minute mixing period. Use narrow
range pH indicator paper if organic material is observed floating on the top of the
slurry to avoid damage to pH electrodes.
C.5. Procedure for alkaline wastes -- if the initial pH of the slurry is > 5.0, add 3.5 mL
of 1N HCI to determine if the alkalinity of the waste is sufficient to require the use
of the stronger acid extraction fluid.
C.6. Neutralization reaction conditions - the slurry should be heated to 50 °C and held
for ten minutes.The laboratory should consider validating their procedure to confirm
these conditions are met. A bench procedure specifying the hot plate setting (or
other source of heat), the time required to reach the desired temperature, the ten
minute time at temperature, and the time required to return to room temperature
should be established. This will assure the maximum degree o.f reproducibility in the
determination of the alkaline potential of the wastes tested.
C.7. Secondary pH — record the pH of the slurry after it has completed the cooling cycle.
D. Selection of Extraction Fluid
D.I. If either the initial pH or the secondary pH is < 5.0, select Extraction Fluid #1 as
the leaching medium.
D.2. If the secondary pH is >5.0, select Extraction Fluid #2 as the leaching medium.
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16
TCLP Worksheet No. 3
Determination of Extraction Fluid Volume
for
Metals, Semi-Volatile Organic Components and Pesticides/Herbicides
Laboratory Sample No.
Reid Sample No.
£. Seierminaijeft of Sampte Size for Usaefc lestmg ~ the metito ,
grarasssapfe sce^orexisrac^on fl[ 7J&5K ;, - ' "" *> % <
1 . particle size reduction? yes/no
2. amount of dry solids (lOOg min.)
3. amount of multi-phasic sample1
a. weight of material
b. weight of filtrate
c. weight of solid material
F. Detersanatian , W*sfcsfce££$icu'2,/ - ;
1 . for dry solids (20X sample wt.)
2. for multi-phasic samples2
&. Record of Exiracfion ^est - tfee exiract«m period is.specilted as 18 ± 2 hears. ,
1 . extraction start time
2. extraction stop time
3. filtration complete time
4. pH of filtrate
5. volume of filtrate
1. The theoretical amount of multi-phasic waste necessary to yield a 100g sample is
given by:
Amount of multi-phasic material =
(104)
(wt percent wet solids)
2. The amount of extraction fluid needed to extract the solid material from a filtered multi-
phasic waste is given by:
Amount of extraction fluid = 20 (weight of material filtered - weight of filtrate)
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17
Discussion and Recommendations
TCLP Worksheet No. 3
TCLP Extraction Procedure
for
Metals, Semi-volatile Organic Components, and Pesticides/Herbicides
This worksheet documents the performance of the TCLP extraction procedure for metals,
semi-volatile organic compounds and pesticides/herbicides.
E. Determination of Sample Size for Leaching — the specified size of sample for the
leaching test is a minimum of lOOg (1 7.2.5). The regulatory control limit for defining if
the waste is hazardous.is based on the levels of analytes reported in the leachate
based on this size sample and a twenty to one (20:1) liquid to solid ratio. If the
amount of waste subjected to extraction is not 100g, than the volume of extraction
fluid must be adjusted to preserve the liquid to solid ratio.
E.1. Amount of dry solids — record the weight of dry solids.
E.2. Amount of multi-phasic sample -- the amount of multi-phasic waste material
necessary to produce a 10Og sample after filtration can be estimated by the
equation:
Amount of multi-phasic material =
(wt. percent wet solids)
F. Determination of the Amount of Leaching Fluid
F.1. Dry solids -- for dry solids containing no filtrable fluids, the calculation of the
correct volume of leaching fluid is straightforward. The amount is equal to twenty
(20) times the mass of solid being leached. Note that the method specifies a 20:1
ratio based on the weight of extraction fluid required (1 7.2.1.1). If the laboratory
elects to use extraction fluid volume, rigorous adherence to the method requires a
one time specific gravity correction to convert the required weight into the
appropriate volume.
F.2. Multi-phasic samples — the method says (f 7.2.11) the percent wet solids can be
used to calculate the weight of extraction fluid used to extract the solid waste
resulting from the filtration of a known weight of multi-phasic waste. The equation
for this calculation is:
Amount of extraction fluid = 0.2 (percent wet solids) (weight of waste filtered)
This assumes there is no subsampling error between the original determination of
the weight percent solid phase (wet) and the subsequent selection of a weight of
-------
18
the multi-phasic waste for filtration and extraction. This is frequently not so. The
nature of many multi-phasic wastes and/or the necessity to use more than one
sample container for the two determinations means that subsamplng error can be
significant. This error can be eliminated if the actual weight of filtered solids is
determined at the time the material is separated for extraction. The equation for this
calculation is:
Amount of extraction fluid = 20 (weight of material filtered - weight of filtrate)
The actual filtration procedure is detailed in f's 7.2.2 though 7.2.8. Requirements
for sample particle size reduction are given in f 7.1.3 and 7.2.10. These should be
followed as closely as the nature of the samples will allow and all departures from
the instructions should be described in the laboratory notebook.
G. Record of the TCLP Extraction Test - the period of the extraction test is given as
18 ± 2 hours (H 7.2.12). Extraction should be started so the resulting slurry can be
filtered as soon as possible after the 18 hours has past. The filtration effectively stops
the extraction process. If the extraction fluid is left in contact with the waste for longer
than the specified period (overnight or over the weekend), the extraction process
continues and may lead to elevated levels of contaminants.
G.1. Extraction start time - record the time and date the extraction begins.
G.2. Extraction stop time - record the time and date the extraction is completed.
G.3. Filtration completion time - record the time and date the filtration is complete.
G.4. pH of filtrate -- while not required by the method, this is a good indicator of test
performance when performing duplicate laboratory analysis or analyzing field
replicates. It can be a reliable measure of sample heterogeneity.
G.5. Volume of filtrate - record the total volume of filtrate collected from the sample.
This value is required to make the appropriate volume corrections when reporting
the results from multi-phasic wastes.
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19
TCLP Worksheet No. 4
Zero Headspace Extraction (ZHE)
Laboratory Sample No.
Reid Sample No.
H. Betejrninatkw 0f San^pfe Sze for Leacfe testing i~*nax«m»B 2$ grams " - ;
1 . amount of dry solids
2. amount of multi-phasic sample1
tTttf 11*. -i.rfV^.n. t^f A.»VWUU^^ *** '!BvV^'^n4«nr4 Cf
» DeterrrJanalwo o* Amount or .extraction ri
1 . for dry solids (20X sample wt.)
2. for multi-phasic samples2
a. weight of material
b. weight of filtrate
c. weight of solid material
ukfKo.l
J« Record of ZHE Extraction Test - the exfiract«m pe*bd Is as 1 & -± 2. nosrs {| 7>3! 12,3?,;
1 . extraction start time
2. starting pressure
3. extraction stop time
4. ^ if positive pressure
5. filtration completion time
6. pH of filtrate
7. volume of filtrate
1 . Determination of amount of multi-phasic sample for extraction:
a. if weight percent dry solids is < 0.5% (from Worksheet No. 1 , B. 4), the waste is
filtered and the filtrate is defined as the TCLP leachate (1 7.3.4).
b. if weight percent wet solids is > 5% (from Worksheet No. 1, B. 4), the amount of
multi-phasic material which should be filtered to yield a 25 gram sample is-given by:
Amount of mutti- phasic material =
x '
(wt percent wet solids)
2. The amount of extraction fluid #1 needed to extract the solid material from the filtered
multi-phasic waste (H.2) is given by:
Amount of extraction fluid = 20 (weight of material filtered - weight of filtrate)
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20
Discussion and Recommendations
TCLP Worksheet No. 4
Zero Headspace Extraction
for
Determination of Volatile Organic Compounds
This worksheet describes the important information regarding the conduct of the zero
headspace extraction (ZHE) of solid waste materials for volatile organic compounds.
Samples containing < 0.5 % dry solids are NOT subjected to ZHE leaching procedure.
They are filtered in the ZHE device and the resulting filtrate is defined as the TCLP leachate
and analyzed directly (f 7.3.4).
H. Determination of Sample Size for Leach Testing — the maximum sample size for this
test is limited by the volume of the ZHE to approximately 25g (f 7.3).
H.1 . Amount of dry solids - record the weight of dry solids charged to the ZHE but do
not exceed 25g.
H.2. Amount of multi-phasic sample — the amount of multi-phasic waste material
necessary to produce a 25g sample after filtration can be estimated by the
equation:
(2.5 x
Amount of mufti-phasic material = - *==
(wt. percent wet solids)
I. Determination of the Amount of Leaching Fluid #1
1.1 . Dry solids - for dry solids containing no filterable fluids, the calculation of the
correct volume of leaching fluid is straightforward. The amount is equal to twenty
(20) times the mass of solid being leached. Note that the method specifies a 20:1
ratio based on the weight of extraction fluid required (H 7.3.1 1). If the laboratory
elects to use extraction fluid volume, rigorous adherence to the method requires a
one time specific gravity correction to convert the required weight into the
appropriate volume.
1. 2. Multi-phasic samples - the method indicates (\ 7.3.1 1) that the percent wet solids
can be used to calculate the weight of extraction fluid used to extract the solid
waste resulting from the filtration of a known weight of multi-phasic waste. The
equation for this calculation is:
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21
Amount of extraction fluid = 20 (Percent wet solids) (weight of waste filtered)
100
This assumes there is no subsampling error between the original determination of
the weight percent solid phase (wet) and the subsequent selection of a weight of
the multi-phasic waste for filtration and extraction. This is frequently not the case.
The nature of many multi-phasic wastes and/or the necessity to use more than one
sample container for the two determinations means that subsamplng error can be
significant. This error can be eliminated if the actual weight of filtered solids is
determined at the time the material is separated for extraction. The equation for this
calculation is:
Amount of extraction fluid = 20 (weight of material filtered - weight of filtrate]
The actual filtration procedure is detailed in f's 7.3.7 though 7.3.9. Requirements for
sample particle size reduction are given in ^ 7.3.5 and 7.3.6. These should be followed as
closely as the nature of the samples will allow and all departures from the instructions
should be described in the laboratory notebook.
The addition of extraction fluid #1 to the ZHE is described in detail in 1 7.3.12.
J. Record of the ZHE Extraction Test -- the period of the extraction test is given as
18 ± 2 hours (f 7.3.12.3). Extraction should be started so the resulting slurry can be
filtered as soon as possible after the 18 hours has past. The filtration effectively stops
the extraction process. If the extraction fluid is left in contact with the waste for longer
than the specified extraction period (overnight or over the weekend), the extraction
process continues and may lead to elevated levels of contaminants.
J.1. Extraction start time -- record the time and date the extraction begins.
J.2. Starting pressure - the method requires the ZHE be pressurized to approximately
10 psi at the beginning of the test.
J.3. Extraction stop time - record the time and date the extraction is completed.
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22
J.4. Positive final pressure - the method requires that the ZHE retain positive pressure
at the conclusion of the extraction period or the test must be repeated H 7.3.13).
Loss of pressure is an indication the ZHE leaked during the test resulting in a loss of
volatile components.
J.5. Filtration completion time — record the time and date the filtration is complete.
J.6. pH of filtrate - while not required by the method, this is'a good indicator of test
performance when performing duplicate laboratory analysis or analyzing field
replicates. It can be a reliable measure of sample heterogeneity.
J.7. Volume of filtrate -- record the total volume of filtrate collected from the sample:
This value is required to make the_ appropriate volume corrections when reporting
the results from multi-phasic wastes. The filtration of oily wastes may be especially
difficult.
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CD
Q.
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Appendix IX
Office of Solid Waste Methods Section
Required Uses of SW 846
-------
The following information regarding required uses of SW-846
was compiled by the Methods Section, OSW, U.S. EPA Headquarters.
Several of the hazardous waste regulations under Subtitle C of
RCRA require that specific testing methods described in SW-846 be
employed for certain applications. Any reliable analytical method
may be used to meet other requirements in 40 CFR parts 260 through
270. For the convenience of the reader, the Agency lists below a
number of the sections found in 40 CFR parts 260 through 270 that
require the use of a specific method for a particular application,
or the use of appropriate SW-846 methods in general:
(1) Section 260.22(d)(1)(i) - Submission of data in support
of petitions to exclude a waste produced at a particular
facility (i.e.. delisting petitions);
(2) Sections 261.22(a)(l) and (2) - Evaluation of waste
against the corrosivity characteristic;
(3) Sections 261.24 (a) - Leaching procedure for evaluation of
waste against the toxicity characteristic;
(4) Sections 264.190(a), 264.314(c), 265.190(a), and
265.314 (d) - Evaluation of waste to determine if free
liquid is a component of the waste;
(5) Section 266.112(b)(1) - Certain analyses in support of
exclusion from the definition of a hazardous waste of a
residue which was derived from burning hazardous waste in
boilers and industrial furnaces;
(6) Section 268.32 (i) - Evaluation of a waste to determine if
it is a liquid for purposes of certain land disposal
prohibitions;
(7) Sections 268.40(a), 268.41(a), and 268.43(a) -Leaching
procedure for evaluation of waste to determine compliance
with Land Disposal treatment standards;
(8) Sections 270.19(c)(1)(iii) and (iv), and
270.62(b)(2)(i)(C) and (D) - Analysis and approximate
quantification of the hazardous constituents identified
in the waste prior to conducting a trial burn in support
of an application for a hazardous waste incineration
permit; and
(9) Sections 270.22 (a) (2) (ii) (B) and 270.66(c) (2) (i) and (ii)
- Analysis conducted in support of a destruction and
removal efficiency (DRE) trial burn waiver for boilers
and industrial furnaces burning low risk wastes, and
analysis and approximate quantitation conducted for a
trial burn in support of an application for a permit to
burn hazardous waste in a boiler and industrial furnace.
-------
•o
CD
D
Q.
x"
X
-------
Appendix X
Stabilization/Solidification: Is It Always Appropriate?
and
Stabilization/Solidification of Wastes Containing
Volatile Organic Compounds in Commercial
Cementitious Waste Forms
Printed with permission from STP 1123 Stabilization and Solidification of Hazardous,
Radioactive, and Mixed Wastes, 2nd Volume, copyright American Society for Testing and
Materials, 1916 Race Street, Philadelphia, PA 19103
-------
»viutb/MNUdAHIHONSOLIDIFICATION/STADIUZA1i^ . 19
Car/ton C. Wiles1 and Edwin Barth*
Solidification/Stabilization: Is It Always
Appropriate?
KKI I:KI;NC K: Wiles. C. C. mid llarlh. r. "SnlliHIIciillnn/SlBblll/nllon: Is II AI»Hys Approprl-
a\tT' Siiil>ili:tiii«ii(inilSl'll«:iirili>iis. RiuliiiiMive. tinil Ali\til ll'axlex. 2ml \'nl-
mm:. I.V'/'.I/ AT/' //.?.*. T. M. (iilliam and C'. C. Wiles. Eds. American Society fur Testing and
Materials. I'hiladclphia. 1992. pp. IK-.12.
A IIS IK ACT: The lindinps of recent research und evaluation efforts arc assessed In determine
whether solidificalion/stahili/mion (S/S) has been pro|>crly and appropriately applied for diffcr-
enl types of hazardous wastes. Kcsulls from these studies are mixed and. as a result, the need Tor
proper lest procedures and for Ircalahilily studies is emphasized. Technical guidance is given Tor
assessing the appropriateness of using S/S for any specific wastes.
KKY WORDS: solidification, stabilization, immobilization, hazardous wnslc, toxic waste, waste
treatment, remediation. Ircalahilily studies
The increasing use of solidification/stabilization (S/S) technologies in lite United Slides.
cspi'dnlly for remediation of sites under (he Supcrfund program, has raised several questions
about the overall appropriateness of S/S. Tor many types of hazardous waste, notably for
heavy metals. S/S usually gives excellent results for long-term immobilization, as measured by
existing physical and chemical protocols. However, results of several studies, as well as dala
from remediation of several Siipcrfund silcs. have raised concerns about whether S/S is a valid
technology for treating organic-bearing wastes, liven when applied to heavy metals. S/S
requires careful choice ofpropcr binders (recognizing the ampholcric behavior of certain met-
als) and good quality control throughout the process. Lack of good investigative procedures
has diminished the value of dala for evaluating S/S for some metals. Furthermore, studies also
provide evidence that tests oilier lhan the regulatory extraction tests (for example, toxicily
characteristic leaching procedure (TCLI')| will be required to evaluate the effectiveness of
S/S, especially when applied to organic wastes. Suggestions are offered for improving treat-
ability studies used for evaluating S/S applied to selected metals. Approaches arc also provided
for determining the appropriateness of S/S applied lo organic contaminants. This paper will
focus on evaluating chemical leaching behavior as a measure of S/S cDcctivcncss.
Mechanisms for Containing Contaminants by Solldlllcallon/Slabillzallnn
Al present, the most prevalently used S/S technologies arc ccmcnl-bnscd or poz/.olan-bascd.
Such processes result in several chemical and physical mechanisms that combine, capture,
and/or immobilize the waste contaminant. The chemical mechanisms ctin include chemical
form change (such as (he chemical change ofa soluble sail of a hazardous melal to a relatively
insoluble silicate, hydroxide, or carbonate form), chemical incorporation within a crystal, sim-
1 U.S. Environmental Protection Agency. Ilisk Reduction Engineering Luhornlory. Cincinnati. Oil
452M.
18
pic adsorption mechanisms, and similar chemical processes. The physical mechanisms
involve (he capture (microcncapstilalion) of hazardous material within the resulting physical
structure of the solidified waste form. Release of physically contained contaminants is
impeded by effects such as a decrease in the permeability and porosity compared to thai ofthc
"native" soil, an increase in Hie tortuosity of escape paths, and decreased surface area. These
physical characteristics aid in eliminating or controlling water transport through the solidified
product and thus the transport of the contaminant lo the environment. However, if the waste
exists (or can exist) in a liquid or gaseous form at ambient temperatures and pressures, then
the possibility of contaminant escape in it form other than in an aqueous solution must also
IK- considered.
Solidiftcation/stabilizalion has been repeatedly demonstrated as an acceptable method lo
immobili/c heavy metal wastes, us well as soils and sludges contaminated with heavy metals.
This treatment technique is not without potential pillalls. Technologies such as pozzolanic
solidification, in which (he hazardous metal is incorporated into an insoluble crystalline struc-
ture of lite solid product, arc probably the most reliable for long-term immobilization. Other
techniques, such as lime stabilization, may not be as reliable. Careful consideration of waste
characteristics versus binder mechanism is absolutely necessary when considering any S/S
process.
The opportunities to capture and contain organic materials in a cement-based solidification
processarc limited. Most organics do not form insoluble precipitates. Moreover, most organic
molecules arc loo large and do not readily enter into the crystal structure of most crystalline
solids. Therefore, sorplion processes and various physical containment mechanisms arc the
major mechanisms that immobilize organics. It should be noted (hat al least one S/S vendor
claims lo have a proprietary chemical (hat incorporates large organic molecules into a clalh-
rale. a structural capture analogous to capture within a crystal.
Evaluations of whether a contaminant has been successfully immobilized by a particular
S/S process arc usually based on how much of the contaminant is removed by nn extraction
test. Tor metals, such extraction tests have been based on aqueous or weak acid extractions.
Test procedures for the evaluation ofthc immobilization of organic materials must lake into
consideration the manner in which organic materials can escape. Most hazardous organic
materials arc only slightly soluble in water or in the weak acids used in the common regulatory
extraction lest procedures. Thus, these tests may measure the ability ofthc material lo escape
in an aqueous medium but not its ability to escape in its liquid or gaseous form. Many organics
are not readily mobile in an aqueous medium and yet can be quite mobile in liquid or gaseous
form. The U.S. Environmental Protection Agency (El'A) is sponsoring studies of test and eval-
ualion procedures (hat may lead to improved technical evaluations of S/S applied lo a broad
range of waste types, both organic and inorganic.
S/S Applied lo Toxic Mela Is
"I he chemical mechanisms for binding and incorporating hazardous constituents into S/S
products arc exceedingly complex. Review of dala from several S/S applications reveals a lack
of consistency in reporting which makes it difficult to interpret and compare results. Further-
more, many S/S technologies on (he market include proprietary additives whose function can
vary from useless to absolutely necessary. The CI'A is supporting research lo further the under-
standing of S/S approaches. F,vcn without a complete understanding of S/S chemistry, it is
obvious that the chemical character of the waste constituents and possible chemical interac-
tions between the waste, (he binder materials, and any interfering chemicals arc of paramount
importance.
l-or example, consider three toxic metals of common concern: arsenic, chrome, and lead.
-------
20
HAZARDOUS WASTES
Arsenic under oxidizing conditions will be in the pentavnlcnt form :md will be soluble over u
broad range of pH values (pi I from » 2 to 14). Thus, in order to stabilize arsenic chemically,
it may be necessary to reduce it to the trivalcnt or elemental form. In this case, the pi! must
be maintained below 11, as As(lll) becomes soluble at a pH of > 11.
Chromium is similar to arsenic in its chemical behavior. The oxidized, soluble form of
chrome is the hexavalcnt form Cr(VI). In order to apply many of the common S/S technolo-
gies, the operator first must chemically reduce Cr(VI) to Cr(lll), which is relatively insoluble
over o oil range of aboul 5 to 13. Again, controlling final pH in the process is necessary because
Cr(lll) is soluble outside this range.
Lcud is amphotcric, (hut is, it is soluble under both basic and acidic conditions. Lead is fairly
insoluble at pH values between 7 and 12 (Fig. I). At a pH below about 7, lead is soluble as
IV ', while at a pH above 12, it can be soluble as anionic plumbalc ion. Chemical reduction
of the lead is ineffective; proper control of pH is usually more important.
100
11
12
7 8 9 10
SOLUTION pH
HO. I — Xnluliiliiiexitfmviul liyilrnxiili'x usll.
WILES AND BARTH ON SOLIDIFICATION/STABILIZATION 21
thS™1,1 Cn° shorrtcormin?do "0| P"*lu«lc »hc use of S/S for these metals, they do emphasi/c
s/vnr /^ rin8^
hi,? 1 SPCC"IC WUSlC StrCUmS |:urth«more. to improve the inlcrprSalion oFlrc-rt
ab hty s udy results, ccrtum guidelines must be followed. Preliminary rulesof ,h mbTor a e !
•ng S/S technology appl.cd to metals, at the bench-scale level, arc as follows.
'' cllcS cnar^SS'" WflStC 7 WC" "S P08*"*-'- ™»''»™teri»'l!«n should include
£ ™.tssr pis1,™ r "ion- physieai pr"'*rtics-
2' !hc±±'£r:''nina''ls !ind lailor lhc hindcr syslcin
3. Perform appropriate extraction tests on the untreated waste to serve as a benchmark for
subsequent data on the treated waste. Report extraction ics, dmTfo o*h trcS a?d
untreated forms. Consider incorporating leaching data into „ .site-specS JoundwJter
4. Analy/e and record pH on the extracts from the untreated waste and treated product
5. Analyze :add,«,vcs for presence of ha/ardous constituents. Identify -'
o al add.t.vcs to establish a quality control program. Carefully ^
6. When reporting Icachate data on treated samples, show the total percent reduction
aclueved and the extent to which simple dilution has contributed lo ,S£
These arc not complete guidelines for performing trca.abili.y studies merely some rules to
S/S Applied Io Wastes Containing Volatile Organlcs
It is common to distinguish organics as volatile, semivolatilc, and nonvolatile
Iso'cnom wrip0lMHls (V?C) arc considcrcd to bc *»* ^ing iiSt
150 C (30 1 P). When one considers the operational steps in the S/S process ii is ohvim« i
dunng the m,xm6 of binder, wmer. and waste, as well as during „ Sg p ro Ss VQCs
tosi because of the mmng and because of any rise in temperature. The KPA's Ollk°o| Air
cpa ccnoogy. c I c o m S/S
mud KM,sedw,|| depend upon the relative levels of volatile* and other con "uempTsen,
'^^
-------
WILES AND BARTH ON SOLIDIFICATION/STABILIZATION
23
22 HAZARDOUS WASTES
The quantities ofsuch organics acceptable lor S/S should IK bused un a risk assessment Tor
the given site ;ind/or on the result ul'a trculahilily study that includes 11 mass balance on the
organics lie fore, during, and alter treatment. The treat-ability study should include a "harsh"
extraction procedure (lor example, total waste analysis) to evaluate the migration of organics
in both treated and untreated material because many organics arc not soluble in water or weak
acid media. The risk assessment should assume that none ofthe'liighesl risk compounds will
be retained by the S/S process and/or that all such compounds will be lost via air emissions
during the S/S processing, unless an air pollution control mechanism is in place. This scenario
is very conservative as it docs not assume any retardation of the compound that can occur by
physical mechanisms in the solidified waste form. Conversely, the mass balance approach will
give some credit for physical characteristics or other bonding mechanisms in the solidified
waste form, liven so, this approach is also conservative In that a total waste analysis (TWA) or
similar extraction procedure requires grinding of the sample. This grinding results in destroy-
ing or altering and reducing the effectiveness of some physical properties that can impede the
release of the organics under actual field conditions. However, we believe these conservative
approaches arc necessary based upon available S/S data as applied to organics and the appar-
ent inadequacies in the sampling, analysis, and extraction tests used to evaluate the treatment
of organics at Superfund sites.
Therefore, except for the case when 100% hazardous volatile constituents are present, the
amount of organics present may not be the most important factor in deciding whether or not
to evaluate S/S as part of the total treatment process. The important factors are the concen-
tration and characteristics of remaining constituents of concern that will require treatment, if
all the volalilcs were removed and/or destroyed. In other words, prclrcalrncnl, removal, and/
or capture and treatment of volatile organic constituents will be required prior to or during S/
S.
S/S Applied lo Wastes Containing Scmlvolallle Organics
Evaluating the effectiveness of S/S processes lo capture and immobilize semi volatile organ-
ics is more complicated. After mixing, the solidification process that lakes place over a period
of time is called "curing." During the curing process, the water present is used in hydralion
reactions. The final solidified waste form, especially Tor cement-based processes, is usually a
monolithic structure incorporating hydraicd silicates and carbonates in an agglomeration of
crystalline structures that incorporate and/or microcncapsulalc the ha/ardous constituents,
the original soils, and any aggregate that may have been added to enhance the product's
strength. Solidification processes are normally exothermic because of the hydralion reactions.
Typically, the heat given oil'is sulhcicnl lo raise the temperature of the matrix by 30 lo 40°C
in the early stages of curing. In cases where kiln dust or other lime-based products (that is. those
containing large amounts of quicklime (CaO)) arc used, temperature rises can be significantly
higher yet. Thus, it is possible (bat some of the low-boiling semivolatile compounds volalili/c
and escape during the curing process.
Once curing is complete, the cfl'cctivcncss of cement-based solidification processes lo con-
tain semivolatile organic compounds is currently unclear. The application of the TCI.I' test to
organically contaminated soils before and after treatment with cement-based solidification
processes in the Superfund Innovative Technology Evaluation (SITli) program has yielded
inconclusive results. This situation is due largely to the fact that the solubility of the organics
in the extraction fluid is so low that even small quantities of these organic contaminants
quickly saturate the TCLP liquid. Thus, no measurable difference between the teachability of
organic contaminants from untreated soils and from (lie solidified soil product can be detcr-
4- " •n.-Mciin. ni'thi; nnihablc mobility of these
contaminants in aqueous-phase leaching processes, it does not address the potential escape of
organics in liquid or gaseous form. Since the liquid and gaseous forms of these organics can
flow, it is not unreasonable lo expect thai escape will occur.
Thus, the same basic approach is probably necessary for semivolatile organics, as is sug-
gested for volatile organics. If the level of nonvolatile and/or inorganic constituent is present
above some agrccd-upon acceptable threshold, then S/S processes will probably he required
as par! of a complete treatment train. Stabili/ation/solidification would follow some earlier
stage of treatment for the removal and/or destruction of the volatile and semivolalile constit-
uents. The levels of residual semivolatile compounds remaining in the waste prior to a solid-
ification process must be determined based on maximum concentration limits allowable for
each such constituent. Note that in this context, S/S technologies should be deemed inappro-
priate for sites contaminated only with volatile and/or semi volatile organic compounds, unless
some speciali/ed S/S process can be demonstrated to be effective. At present, such demon-
stration should he based on a TWA and should include a mass balance for the waste constit-
uents. As staled earlier, protocols for evaluating S/S applied to organics are presently being
evaluated by EPA.
Discussion of Kxtrnetlon Tests
Extraction tests are used lo determine or estimate the levels of targeted contaminants that
can be extracted from waste under selected conditions. None of the presently existing leach
tests were developed for, nor validated for use in, assessing the teachability of organic com-
pounds. Table I lists several leach tests and some comments on their applicability for organic
contaminants. Technically, the TCI,I' and similar extraction test methods are not adequate
for identifying all classes of organics that might be available for escape to the environment.
The harsh extractions, such as total waste analysis, do not represent realistic field conditions
nor do they recogni/e immobilization due to the physical characteristics of the solidified waste
form. What is needed is a leaching method sensitive to all phases of organics that arc not ade-
quately bound in the solidified matrix. This lest also needs to represent realistic field condi-
tions and be relatively easy lo perform. Unfortunately, no such test currently exists. However,
El'A is investigating potential test methods for this purpose.
Calilwell, Cote, and Chao (/ ] have developed leaching procedures based on sequential batch
leaching, with the development of a partition coefficient between the solid and liquid phases.
The technique appears to work well for low levels of organic contaminants (up to 1000 pg per
gram of solidified waste), but does not fully address the concern about escape in a nonaqucous
medium. Through P.I'A support, the U.S. Army Corps of Engineers, Waterways Experiment
Station and others have performed several studies aimed at evaluating different leach proce-
dures for use in solidification of organic contaminated soils and sediments (--•/). In general,
this'work indicates (hat a sequential batch extraction process gives a better measure of the total
teachable quantity of contaminants present than do the single-exposure tests.
Summary of Selected Results for Organic Wastes
Several studies have been performed that strongly indicate the inadvisahilily of using S/S as
the principal remediation technology for organic wastes. Kolvites and Ilishop |.5| conducted
column leaching tests on cement-based solidified samples containing known amounts of phe-
nol and trichloroethylene (TCI;). So much of the TCI- was lost in preparation and mixing !!'•'!
the results were inconclusive. However, the results for phenol give a good i;i'.-:>."" ' '--r
amount of this semivolalile organic compound that is retained in the solidilki! ••
2 gives the leach lest results on a sample that was allowed lo cure for line. ,..,)-.. am! Taitic ..
-------
24 HAZARDOUS WASTES
TAIlLli I — Siimv exlrarlinn U'.t
Peer Reviewed
Extraction for Organic
Tests Stabilisation
uxt'il fur naliHiliiiR .•stul>ilizuiiiin/\i>liilij'uiaiii»i til 'nrifiinic-
ctinuiminalfd nvi.v/c.
WILES AND BARTH ON SOLIDIFICATION/STABILIZATION
TAHI.I-: 2—Mnxx Imlanrc: Iruch li-xl No. I |5|.
25
Utilized for Evaluating
Organic Stabilization
Comments
TCLP
1 CLP Cage
No
No
TCLP Acid
Rain
TCLP Acetone
MEP
Total Waste
Analysis
(TWA)
ANSI 16.1
ANSI 16.1 plus
groundwatcr
Acid Rain
(1312)
No
No
No
No
No
No
No
Several Supcrfund
Sites
ASTM Committee
D-34
Limited number
of Supcrfund
sites
Limited number
of Super fund
sites
Delisting (metals)
R&D
Several SuperCund
sites
Limited number
of Superfund
sites
Unknown
Grinding or monolith,
Codisposal scenario only may not
show organics
Most organics not soluble in
Icachatc
No grinding
Erosion caused by cage docs not
represent "real world"
Poor rcproducibility noted by
ASTM
Most organics not soluble in
Icachole
Used synthetic acid rain with TCLP
apparatus
Acetone to extract PCBs nut
realistic
Conservative worst case docs not
represent "real world"
Somewhat realistic
Simulates acid rain
Mclliylenc chloride or hexanc
Conservative worst case, docs not
represent "real world"
May not show organics
May not show organics
May not be representative of real
acid rain
May not be applicable Tor organics
Tor a sample that was allowed to cure 28 days before leach testing. These tables show u com-
plete mass balance indicating the amount of phenol retained in the solidified product. The
enhanced retention in the 28-day cured product is probably due to a decrease in pore size in
the product as curing proceeds. Twenty-eight days is a typical curing time for cement-based
solidification processes. Even so, only about 40% of the phenol is retained in the solidified
product.
Bricka, Holmes, and Cullinane \6\ of the U.S. Army Corps of Engineers, Waterways Exper-
iment Station, in a study performed for EPA, showed a comparison of the EP and TCLP leach-
ing extracts for two solidified sludges and one nonsolidificd, organic-based sludge (Table 4). A
metal hydroxide sludge (identified as WES) was stabilized by addition of cement. A second
material (identified as WTC) was a metal solution containing chromium chloride, cadmium
nitrate, Jr 'ate, sodium arsenite, and phenol at a pi I of 2.5. This synthetic metal solution
was sol\ / adding Portland cement. Type F fly ash, and soil in equal quantities to the
• ' - . Thn ihirrt material, n PCE sludge, was a still-bottom waste resulting from the
Leaching Period
Days 1 and 2: Icachiilc
vnpor
Days 3 and 4: Icachatc
Dnys 5 and 6: Icachatc
Days 7 and 8: Icachalc
vapor
Total phenol leached from 30 g of cement product
Phenol adsorbed to liner of cement mold
Phenol mixed into 30 g of cement product
Phenol retained in cement product (calculated by difference)
I'hcnol
Released, nig
27.42
6.13
2.54
1.04
0.00
37.13
0.05
40.00
2.74
1. enchant
Volume, ml.
245
339
385
377
distillation of "dirty" perchloroclhylcnc for solvent recovery. Each of these wastes wits spiked
with 1000 to 10 000 mg/L of twelve organic compounds and then treated. The treated mate-
rials were then subjected to the two extraction procedures and their Icachatc analyzed. The
data presented in Table 4 show that, except for the polar compounds butanonc and 4-methyl-
penlanonc, less than 3% of the spiking contaminant was recovered in either extract, even from
the nonsolidified PCE organic-based sludge. This result clearly indicates that uqucous-phnsc
leach tests arc not truly measuring the potential for escape of low-solubility organic
compounds.
In an attempt to enhance the capture and retention of organic materials in cement-based
solidified waste. Sheriff'el al. [ 7] of the Imperial College of London added activated charcoal
and various clays to specific organic waste streams prior to cement-based solidification. Figure
2 is an example of the results of mixing 40 g of cement with I g of charcoal and 40 mg of phenol
and two chlorinated phenols. The controls indicated on the graph arc the same concentration
of organic contaminants in cement nlonc with no charcoal added.
In a study evaluating the loss of volatile organic material during solidification, Wcilztnun
et al. 18] presented several graphs showing the loss of specific volatile organic compounds dur-
ing mixing and curing. Figure 3 is typical of their results and shows the results for two solidi-
TABI.n 3—Mass Imltimr: Itwli li-xl Ni>. }. |5|.
Leaching Period
Days 1 and 2: Icarhalc
Days 3 and 4: Icnchate
Days 5 and 6: Icachalc
Days 7 and 8: Icachutc
Total phenol leached from 30 g of cement product
10! mixed into 30 g of cement product
iol retained in cvnient product (calculated by difVcrencc)
I'hcnol
Released, mg
13.54
0.00
5.08
0.00
3.08
0.00
1.60
23.30
40.00
16.68
l.vuchanl
Volume, mL
245
228
219
192
-------
26 HAZARDOUS WASTES
WILES AND BARTH ON SOLIDIFICATION/STABILIZATION 27
TAni.l:4—Cimliiwcd
Sludge
wt:s
PCI;
WTC
wns
per.
WTC
wi:s
PCF.
WTC
wrs
per.
WTC
wi-:s
PCI-
WTC
Wl-S
PCF.
WTC
Wl-S
Level of
Spike Added,
mg/L
I 000
10000
I 000
10000
I 000
10000
I 000
10000
I 000
10000
I 000
10000
1000
10000
I 000
10000
I 000
10000
I 000
10000
I 000
10000
1000
10000
I 000
10 000
1000
10000
I 000
10000
I 000
10000
I 000
10000
I 000
10000
I 000
10 000
__, . —
Extract Concentration.
mg/L
CP TCI.P
__
CHLOROFORM
A flfl 1 40
O.oH I.HU
n 0-7 27 27
1 J.V / £.§.*.*
i ni 1 56
1.0! '-JU
11 -n 12 70
Z J. / / •**-• '"
0 22 0-20
8.98 9.13
1,2-DlCIILOROETIIANE
1 <7 1 27
1 .5 1 '•*•'
iu in f\i M
JO. /U «• ••' '
i/»i 421
J.0 1 -?.*•••
5730 71-40
o 76 0 49
U. IU !/.-»'
45.03 44.23
1 , 1 , 1 -TRICII I.OHOKTII AMU
n at. 1 93
U.VO I.'-*
iu 11 4(, 80
I n. J J f w.««
0 55 4-"°
nm 2507
1 J.U / f.j.w
029 0.45
I5'.07 24'.83
CARBON TETRACHLORIDE
n At 0 89
U.*l- v/.o'
393 7-60
023 ".SO
in /in 1000
IU.UU '"• w
/> in 0 20
U. Ill VJ.tu
5.00 5.00
TRK-III.OKOETIIKNF.
3 47 6.90
,". A1 1 14 11
64. 6J i .»**.. '-'
1 48 3-54
3373 39-97
232 2.55
98'.()7 135.67
IlLN/ENF.
l.ftO 2.30
42.97 R5.33
_ . — e m
2.62 5.29
54 17 76.57
091 0^79
55.23 62.40
1,1.2,2-TUIC-IILOROIiTIIANl:
/i T« (k 22
O.iJ "•"
1 00 5.00
7.31 'MM
nvi'nitfi'tl twr tnc
_ • —
"'"'''
Organic Recovery, %
,,•
0.088
0.140
0.101
0.238
0.022
0.090
0.157
0.387
0.361
0.573
0.076
0.450
0.096
0.183
0.055
0.151
0.029
0.151
0.042
0.039
0.023
0.100
0.010
0.050
0.347
0.646
0.148
0.337
0.2.32
0.981
0.160
0.430
0.262
0.542
0.091
0.552
0.025
0.010
0.7.31
TCI.P
0.140
0.273
0.156
0.327
0.020
0.091
0.127
0.614
0.423
0.714
0.049
0.442
0.193
0.468
0.480
0.251
0.045
0.248
0.089
0.076
0.050
0.100
0.020
0.050
0.690
1.343
0.354
0.400
0.255
1.357
0.230
6.853
0.529
0.766
0.079
0.624
0.022
0.050
0.904
l\ 1IW.
lixlracl Concenlralion,
Level of mg/l. Organic Recovery. %
f. •! All 1
bplKC AlIUCU,
Sludge mg/l- I:P TCI.P I-P TCI.P
WTC 1000 0.10 0.20 0.010 0.020
10000 ,5.00 5.00 0.050 0.050
TliTKAC-tll.nRUKTIIF.NK
WPS 1000 3.10 7.00 0.310 0.700
10000 25.97 38.67 0.260 0.387
PCI 1 000 3.03 3.19 0.303 0.319
10(1110 28.30 13.37 0.283 0.134
WTC 1000 1.00 1.60 0.100 0.160
18.87 39.87 0.189 0.399
TOLUENE
WI:S 1 000 3.03 4.43 0.303 0.443
10000 55.43 93.67 0.554 0.937
PCI- 1000 1.37 2.50 0.1.37 0.250
36.67 35.77 0.367 0.358
WTC 1000 1.24 1.39 0.124 0.139
10000 65.67 89.57 0.657 0.896
HTPIYI m;N/HNH
WI-1S 1 000 5.27 17.33 0.527 1.73.3
10 000 33.83 47.33 0.338 0.473
PCI- 1 000 2.03 2.33 0.203 0.233
10000 34.53 20.93 0.345 0.209
WTC 1 000 2.93 3.94 0.29.3 0.394
10000 36.10 95.60 0.361 0.956
HUTANONE
WliS 1000 .35.80 17.00 3.580 1.700
10000 188.00 256.67 1.880 2.567
PCr. 1000 5.19 5.39 0.519 0.539
100(10 1.33.33 134.33 1.333 1.343
W 1C 1 000 9.59 6.29 0.959 0.629
10000 163.00 165.67 1.630 1.657
4-MiniiYi.-2-PnNTANONi;
WliS 1000 41.3.3 13.33 4.133 1.3.33
10000 192.67 313.33 1.927 3.133
PCI: 1000 11.63 10.63 1.163 1.063
10000 2.33.00 247.00 2.330 2.470
WTC 1 000 7.67 4.88 0.767 0.488
298.00 306.00 2.980 3.060
fkiUion processes, one based on porllatul cement and lly ash, (he other on lime kiln dust and
fly ash. Holl) are compared with a blank wherein the organic materials were mixed with non-
reactive solid material to .simulate the solidification mixing process. This work and additional
field tests are being used by LPA to develop regulations and guidance on the control of VOC
emissions during S/S treatment processes used at KCKA TSD facilities.
decently, research with modified clay has shown promise for a strong Bonding hcluvcu
scmivolalile compounds and organophilic clay material |'Jj. The extraction dula presented in
Table 5 and bonding evaluation icclinkiuc.s indicated .strong bonding.
-------
28 HAZARDOUS WASTES
• phenol
40_> • 3-chlorophenol
WILES AND BARTH ON SOLIDIFICATION/STABILIZATION 29
TAIll .1: 5—KMniiliiin itnlii mniil imv/c Mahilizal willi iirntint>l>liilii' rluvx.
00
23456789
TIME/DAYS
IIG. 2-/..W/. (.•<» .m iwiiiii amiainiw '" ' ~ to col-.
led and treat the organics as part of the S/S treatment train.
-------
HAZARDOUS WASTES
Does The Site
Contain Orgonlcs ?
no,
•»•—i
,yes
Are Organlcs Above
"Levels of Concern" f
no
Consider S/s|
f yes
Does The Site
Organlcs ?
I yes
Are The Organlce
Mobile, Volatile,
Semi-Volatile,
Or Soluble ?
Are There CandU
S/S Processes F<
Treating Such
Organlcs
no
no
— lyes
-------
HAZARDOUS WASTES
Acknowledgments
The authors wish lo thank Or. Joseph T. Swnrlzbnugli. PEER Consultants. P.C.. and Dr.
Jeffrey Means. Hnllcllc Mcrnorinl Institute, Tor their assistance in preparing this paper.
References
|/| Cote. P. I.., Caldwcll. R.. and Chao. C. C., "Physical and Chemical Containment of Organic Contam-
inants in Solidilicd Waste." IIVi.«r MtiiHiRi-nn-iil. Vol. 10, 1991), pp. 95-102.
(.?) Shivcly. W. E. mill Crawford. M. A. in Knvinminenial Aspects iif'.Siiil>ili:iiliiin anilSolidificationof
Hazardous and Radioactive II 'asles. ASTM SIT 10.13.1'. I.. Cote and T. M. Gilliam. Hds., American
Sncicly for Testing ;md Materials. Philadelphia. 1989. pp. 150-169.
[.<) Slcgcniunii. J. and Cole. P. I... "Investigation of Test Methods for Solidified Waste Evaluation—A
Cooperative Program," Report UPS 3/11 A/8, Woslcwntcr Technology Center, Environment Canada,
Burlington. Ontario. January 1991.
\4\ Bricka. R. M.. Holmes. T.. and Cullinanc. M. J.. "An Evaluation of Stabilization/Solidification of
Metal Hydroxide Sludge (F006)." Technical Report EL-8H-XX. U.S. Army Engineer Waterways
Experiment .Station. Vickshurg. MS. 1987.
\H] Kolvitcs, II. and Bishop. I'.. "Column Leach Testing of Phenol and Trichloroclhylcnc Stabilized/
Solidified with Portland Cement," Knvironmemal Aspects of Stabilization and Solidification of llai-
ardmis and Radioactive II Vi.«i'.t. ASTM .977' 10}J. P. Cote and M. Gilliam, Eds. American Society
for Testing ami Materials. Philadelphia. 1989. pp. 238-250.
|rt| Rricka. R. M.. Holmes, T. T., and Cullinanc, M. J., "A Comparative Evaluation of Two Extraction
Procedures: The TCLPand the EP." USEPA, Cincinnati. OH, in press. 1990.
[7| Sheriff. T. S.. Sollars. C. J.. Montgomery. D.. and Perry, R.. "The Use of Activated Charcoal and
Tctra-Alkyl Ammonium-Substituted Clays in Ccmcnl-Dascd Stabilization/Solidification of Phenols
and Chlorinated Phenols." Knvironmental Aspects of Stabilization and Solidification ofHazardum
and Radioactive Wastes. ASTM SI T1033. P. L. Cote and T. M. Gilliam, Eds.! ASTM, Philadelphia.
1989. pp. 273-286.
|.V| Wcilzman. I... Hamcl, L.. and Cadmus. S., "Volatile Emissions from Stabilized Waste." final report,
U.S. EPA Contract 69-02-1993. WA 32 and 37. Risk Reduction Engineering laboratory. Environ-
mental Protection Agency. Cincinnati. OH. 1988.
(°| Soumlnrarajan. R. and Darlh, E., "Using an Organnphilic Clay to Chemically Stabilize Waste Con-
taining Organic Compounds." Hazardous Materials Comrol Journal. Vol. 3. No. I, 1990.
Rcngarajan Soundararajan'
Guidelines for Evaluation of the Permanence
of a Stabilization/Solidification Technology
REFKHKNCE: Soundararajan. R.. "Guidelines for Evaluation of (he Permanence of a Stabili-
zation/Solidification Technology," Stabilization and Solidification of Hazardous, Radioactive.
and Mixed Wastes. 2nd Volume. ASTMSTI' 1123. I. M. Gilliam and C. C. Wiles. Eds., Amer-
ican Society for Testing and Materials. Philadelphia, 1992, pp. 33-39.
ABSTRACT: Stabilization/solidification technologies are used widely for treating both inor-
ganic and organic waste materials. Unfortunately, some of these processes have turned out lo be
simple adsorption/dilution phenomena. For a true stabilization/solidification process, the
hinder and the waste must interact chemically to create chemical bonding. Based on our past
investigations In this area, some guidelines for evaluating the permanence of a stabilization/
solidification process arc presented in this paper.
KKY WORDS: stabilization, solidification, adsorption, dilution, chemical bonding. Fourier
transform infrared spectra (FTIR), Ihermogravimelric analysis (TGA). differential scanningcnl-
orimelry(DSC), bond energy, heat of solution
Stabilization/solidification (S/S) technologies are emerging as viable alternatives for other
waste management processes. However, there have been a number of questions raised about
the technology's effectiveness and permanence by the Office of Technology Assessment. Sev-
eral reports critical of the "science" involved in this process have been published in the recent
p.isl. It becomes imperative lo take a hard look at the technology from a purely scientific stand-
point and lo gather evidence nbout the permanence of this process in order to preserve the
integrity of the technology. In the past, we have conducted a scries of investigations on various
aspects of S/S technology. Based on our findings, we present a few protocols that would assess
Ihc permanence of an S/S process. Most of the research work presented in this paper was
funded by (he Office of Research and Development of the U.S. Environmental Protection
Agency (EPA), Cincinnati, OH.
Discussion
It is worth mentioning that nil S/S technologies are governed by the fundamental laws of
chemistry. A thorough understanding of (he chemistry of the waste lo be stabilized results in
a belter stabilization process. In general. Ihc S/S process of inorganics and organics may be
explained as follows: In Ihc inorganic S/S process, the metallic ion to be fixed is converted into
its most insoluble form and then placed inside a cemcntitious matrix (/J.
In Ihc case of stabilization of lead, for example. Ihc following facts were considered. The
solubilityproductorieadhydroxide|Pb{OH),Jisknowntobe 1.2 X I(T'5. We need this infor-
1 Director, Research and Development. RMC Environmental and Analytical Laboratories. 214 Wesl
Main Plaza. West Plains, MO 65775.
33
-------
HAZARDOUS WASTES
\4\
|.<|
|fi|
\7\
[cf|
| V]
| If)]
(//)
1 12]
| If |
1 1 ft)
1 17]
1 18]
[IV]
[20]
DC Pcrcin. P. It. inul Sawyer. S.. /Vnrm/i/i.v.v t>f Research Syinikisiuiii mi IMII! Disintxiil. Remedial
Aciicin. liiciiierdiinii and I'minncm <>l lla:l Kcsciurli fiymimxiuni. hunt Dispmul.
Remedial Action. IncincrnliiHiiind Treatment at Hazardous ll'iisle. V«il. 14. l;PA/600/9-88/02l.
U.S. I'livironmctiliil Protection Agency. C'incinniili. Oil. July I')HK, pp. 542-557.
Weil/man. I... llamcl. L. l:... IX- Perdu. I'., iiiul Ulancy, U.. I'riimtlintis iif Ki'xi'uri'll Si'm/msinm.
' l.nnil l)i\in>.\ul. Ki'tiifiliiil Action. Incineration unit Trmlmcnl iil'Ha:anliiiix ll'iisle. Vol. 1 5, 1- PA/
(i()()-9-90/()l)ri. U.S. l-nvirotinicnlal I'rolccliiu) Agency. C'incinnali. OH. Id). I ')')(), pp. 448-458.
Knwc. Ci.. "Evaluation of iK-nlnicnl Icchnnliigics lor Listed Petroleum Refinery Wastes. Final
Keport." No. 4465. American Petroleum Institute. Washington. DC. May I9KK.
(iihhons. J. J. and Soundararajan. K.. Anwriain l.iihiiriitury. Vol. 20. No. 7. July I «S8, pp. .18-46.
Ciihbons. J. J. nnd Snundararajan. R.. American Liilinriiliiry. Vol. 21. No. 7. July I9K9, pp. 70-79.
Soundararajan. K.. Hurtli. i;.. aiiilOililnins. J. J.. Hn:iinli>ii.nncninl Science unit Teehnnhtgv. Vol
17. No. 4. IV83. pp. 227-230.
lloyd. S. A.. Shaohai. S.. Lcc. J.-l7.. and Mortland. M. M.. Ctavx anildav Minerals. Vol. 36. No. 2.
1 988. pp. 125-130.
McRridc. M. n.. Pinnavaia. T. J.. and Moilland. M. M.. in I'ule nf I'nlliiltinlx in the Air nnd Water
lim-ininineiilx. 1'iin I. John Wiley and Sons. New York. 1977. pp. 145-154.
Mortland. M. M.. Shaohai. S.. and Boyd. S.. CYnr.v anil Cluv Minerals. Vol. 34. No. 5. 1986, pp.
581-585.
Sheriff. T. S., Sollars. C. J.. Montgomery, D.. and Perry R., Knvinmmenlal Teflumltinv tellers. Vol.
8. 1987. pp. 501-514.
Hishop. P. I... Hazardous \\astcantl Hazardous Materials. Vol. 5. No. 2. 1988, pp. 129-143.
Maishall.C. (:.. '//«• I'lmical Cheiiiislrr ami MineralnKViifSdih. 1'iiliime I: Xiiil Materials. John
Wiley and Sons. New York. 1964. pp. 260-287.
Roger D. Spence.' T. Michael Gilliam,' Ivan L. Morgan,' and
Steven C. Osborne*
Stabilization/Solidification of Wastes
Containing Volatile Organic Compounds in
Commercial Cementitious Waste Forms
RKKKRKNCK:Spence, R.D..Ciilliam.T.M.. Morgan. I. L.nndOshornc S C "SlablllMlInn/
SoUdineatlon of Waste., Containing Vo.ati.e Organic Compound, In Commerce?£S 2
Waste frorms .S,« MvaummH! Midifitrnhm oj Hazardous. Radioactive, and Mixed Wam*
• !i M"? *? nVV ',('& ™" Gi"iam and C'C' Wilcs' Cds- Amcri"» Society for Vest
ing and Materials. Philadelphia. 1992, pp. 61 -72.
ABSTRACT: Stabilization/solidification (S/S) is one of the most widely used Icchniaucs for
waste treatment and remedial actions, but does not have regulatory approval for treating organ
,«. Apphenlion with volal.le organic compounds (VOCs) is particularly controversiaKh
«as beheved that the^necessary mechanical mixing and exothermic cementitioul reaction
, «...^... ....n.iig nnu vnuinciniic cemcniilious reactions
would vapoii/.c the VOC's the objective of this study was to establish whether S/S is a viable
alternative for a sludge heavily contaminated (about 1%) with relatively immobile metals, but
lightly contaminated (<0.04%) with VOCs that were contaminating the groundwatcr. The mass
balance indicated that > 50%oflhc VOCs were retained in the laboratory preparation ofccmen-
litious samples cured Tor 28 days. The performance tests indicated the commercial products
could attain teachability Indices from 7 to >9 for the eight VOCs studied and distribution coef-
ficients of > 10 could be attained for all eight and > 100 for some compounds.
KKV WORDS: stabilization, solidification. VOCs. organic, immobilization, cement, grout.
waste form. Iricliloroclhcnc, acetone, methyl ethyl kctonc. 1,2-dichloroclhenc. chloroform, ben-
zene, chloroticnzcnc. pcrchlorocf Itcnc
SliihiliKition/solidificalion (S/S) is one of the most widely used techniques for the treatment
and ullimaledisposal ofholh radioactive nnd chemically hazardous wastes because of low pro-
cessing costs, compatibility with a variety of disposal scenarios, and ability to meet stringent
processing and performance requirements. S/S is accepted as the best demonstrated available
technology (BOAT) for many applications involving metals contamination, but not involving
organic contamination [1.2]. The sludge used in (his study was contaminated (sec Table I)
mainly with metals, to u lesser extent with scmivolatilc organics. and to an even lesser extent
volatile organic compounds (VOCs). Only the VOCs were observed to be migrating in the
proundwalcr at the site from which the sludge was excavated: hence. VOCs were the focal point
of the study. In situ S/S is an attractive remedial action alternative in this case because incin-
eration will result in little or no volume reduction for this sludge, incineration may result in
more mobile metallic species, excavation may result in evaporation ofmost of the VOCs. and
in situ S/S may achieve the environmental protection desired with (he least disturbance to the
site and environment and the maximum protection to operating personnel nnd residents. To
pursue this alternative, the sponsor needed to demonstrate the immobilization potential oflhc
1 Chemical Technology Division. Oak Ridge National laboratory. Oak Ridge. TN 37831 -77,7.1.
61
-------
62
HAZARDOUS WASTES
SPENCE ET AL. ON VOLATILE ORGANIC COMPOUNDS 63
TABLE I—Mensurnl n>mviilnilinii.i in lite iins/iikeil\liuliii'.
(Nun-: Sunn' volulilcs nvre lost in tin- profess t>l e.mivating and
ln>nii>xeiii:iiiK tin1 large xinnple. Tht table values reflect wlim »'a.\
present in tlie lalinruliiry prior n> spiking.)"
Compound
Concentration,
mg/kg
Site
Maximum
VOLATILE ORGANIC COMPOUNDS (VOC)
Acclone 1.7 9
1,2-DCt 0.02 100
Chloroform 1.7 17
MCK $.6 4
TCP. 15 130
Dcnzcnc 0.55 3
PP.RC 7.5 59
Chlorobcnzcnc 3.9 20
BASE/NEUTRAL/ACID ORGANIC COMPOUNDS (DNA)
Phenol 3.7
1,3-Dichlorobcnzcnc 130
1,4-Uichlorobcnzcne 120
1,2-Dichlorohcnzcnc <6.l
2.4-Dimcthylphcnol 110
1.2.4-Trichlorohcnzcne 100
2-Mclhyln:iplilhnlenc 190
Di-n-butylphlhulalc • 160
Bis(2-clhylhcxyl)phihalutc 190
METALS
Barium
Cadmium
Chromium
Lead
Silver
Nickel
Aluminum
Calcium
Iron
Phosphorus
Silicon
140
560
6200
760
4.7
210
28000
3000
82 ODD
5401)
1 500
" A 46.4 w(% loss wits observed upon drying the unspikcd
sludge.
commercially available waste forms. Fortunately, recent investigations have indicated true
bonding between organic wastes and sonic binders as required in the Environmental Protec-
tion Agency's (EPA) interpretation of the Hazardous and Solid Waste Amendments (I ISWA)
to Ihc Resource Conservation and Recovery Act (RCRA) (1.3.4].
This paper presents the results of a study done at Oak Ridge National Laboratory (ORNI.)
on the VOC immobilization potential of commercial ccmenlitious waste forms through the
Hazardous Waste Remedial Actions Program (HAZWRAP) in support of Ihc sponsor.
Although the toxicity characteristic leaching procedure (TCI.P) is the regulatory lest Tor these
organ its, it was not considered a satisfactory test of the immobilization potential for these
waste forms because this test was not designed for waste that had been slabili/.ed/solidilied,
and, at the time of this study, regulatory guidance was nol clear on sample handling and prep-
aration when VOCs were involved (that is, VOC losses prior to the initiation of Ihc extraction
procedure may have given erroneously good results). A static leach test was utilized that
enabled the calculation of both the mass transfer resistance ofthc waste forms and the affinity
of the waste forms for the VOCs. Crucial to the accuracy of this test was the development of
techniques to estimate the VOCs actually retained in the sample at Ihc start of leaching. This
was accomplished indirectly by measuring the VOCs that evaporated during sample prepa-
ration. Although the 1 CLP was done and is reported in this paper, the main measure of immo-
bilization potential is considered to be the Icachability index and distribution coefficient
reported for each VOC and each ofthc following four vendors: Vendor A. RMC Environ-
mental and Analytical Laboratories Co.; Vendor B, Wastcch, Inc.; Vendor C, International
Waste Technologies; and Vendor D, Silicate Technology Corp.
Procedures
It is standard practice in studies ofthis type to compare the TCLP performance ofthc waste
before and after treatment. This approach was not used in this study because much of the
VOCs were lost in the process of Inking the large sample needed, and the objective of the study
was measurement of the VOC immobilization potential. In the former approach, it is quite all
right, desirable even, to have Icachntc, or extract, concentrations below the detection limits as
a gross measure of effective Ircatmcni for a specific site; but one learns little about the true
immobilization potential of a particular waste form that can be extrapolated to other condi-
tions or sites. Since the VOC concentration ofthc waste sample in the laboratory was nol rep-
resentative ofthc site VOC concentration, spiking of the laboratory sample was required, and,
to ensure obtaining measurable concentrations in the Icachatcs, spiking was designed to give
concentrations not only higher than the site average concentrations, but also higher than site
maximum concentrations. Eight VOCs—acetone, 1,2-dichloroclhcnc (1,2-DCE). chloro-
form, methyl ethyl kclone (MEK), benzene, irichlorocthcne (TCE), chlorobcnzcnc, and
pcrchloroclhcne (PERC)—were selected among the possible candidates to be spiked into the
sludge and studied.
Sample I'ri'iitiraliun
The procedure consisted of spiking the sludge using a llobart mixer outside the glove box.
taking three sludge samples for analysis by standard U.S. Environmental Protection Agency
(EPA) Contract Laboratory Program (CLP) protocols (EPA CLP Statement of Work for
Organics Analysis Multimedia, Multicomponcnl). immediately placing the spiked sludge
inside the glove box, mixing the spiked sludge with Ihc vendor materials according to Ihc ven-
dor instructions (grout), filling the stainless steel molds with the grout anil covering with stain-
less steel endplales, removing the molds from the glove box and quickly scaling inside Ihc
stainless steel curing pipe, measuring the VOC' concentration of the glove box air using a gas
chromniograph wiih a llame ioni/ation detector (CiC-l ID), curing the samples for 28 days,
measuring the VOC concentration of the curing pipe air with the GC-lrIO, removing (he cured
samples from the pipe, and quickly removing the endplatcs. weighing, and sealing inside a
zero-hcadspace extraction vessel (ZHEV). (Grout means the ccmentitioiis waste form in this
document.) The amount of VOCs retained in the sample prior to leaching was estimated by
subtracting the amount of VOCs that evaporated into the glove box and curing pipe from
Ihe amount measured in the sludge by the EPA protocol. (Rubbers and plastics, including
Tcllon*. should be avoided.)
-------
64 HAZARDOUS WASTES
Sitnic I. caching
The static leaching procedure consisted of suspending each cured sample in 603 gof deion-
izcd water inside a ZIIEV. liuch sample consisted or a tint disk (6.2-cm diameter by 1.6-cm
thick) inside a stainless steel ring with no covering on cither flat race (the leaching surfaces).
Two types of static leaching were done. First, three samples were leached separately Tor the
entire time period with periodic in-house Icachatc analysis. Second, five separate samples were
leached, each For a different time period. At (he end of the time period, the Icuchate was
removed and submitted to an EPA approved laboratory Tor analysis.
Lcachaie Analysis
The in-house analysis was done using a Tckmar liquid sample concentrator (LSC) in con-
junction with a Pcrkin-ElmcrGC ion trap detector (ITD)capahlc of measuring concentrations
as low as I mg/Mg (PPB) within 1 5% of (he true value. The submitted samples were measured
using an I.SC with GC mass spectrometer following EPA contract laboratory procedures
(CLP), capable of measuring concentrations us low as I mg/Mg within 10% of the true value.
Results
Grout Composition anil Properties
Only about 10 to 50% of the VOCs added during spiking was mixed into and retained in the
sludge; presumably, the remainder evaporated during the process of mixing the spike into the
sludge. This was expected based on the development tests and was the reason analysis of
the sludge VOC concentration was required after spiking. The sludge analysis technique con-
sisted of extraction followed by analysis of the extract. The cxlraclanl (typically hcxanc) did
not always extract all of the VOCs in the sludge; thus, the VOC content of the spiked sludge
tended to be underestimated lor this study. Tables 2 and 3 list the average VOC concentra-
tions, and their standard deviations, measured in the spiked sludge used to make the static
leach samples and the TCLP samples, respectively. The acetone concentration was left as an
unknown for the Vendor A static leach samples because its concentration was measured to be
negligible, well below the amount that leached during the static leaching, '('he concentrations
listed in Table 3 were more representative of maximum site concentrations, as intended. The
concentrations listed in Table 2 were designed to give measurable Icachatc concentrations dur-
ing static leaching.
TABLE 2 — Tin- VOC sludge ammunitions meaxiired after spikinxfor the xliilif leai'h samples.
(averane uf three with llie sluiuluril ili-viutiim in parentheses).
Compound
Acetone
1.2-DCI-
Chloroform
MI-K
TCK
Hcruene
PKltc:
Chlorobcnzcnc
Vendor A
a
927(139)
1033(125)
253 ( 69)
623 ( 56)
787 ( 98)
963(119)
550 ( 51)
Vendor I!
I23( 25)
I70( 16)
190 ( 16)
l.17( 9)
193 ( 12)
I73( 17)
537(115)
547 ( 52)
Vendor C
223 ( 9)
485 (304)
313(180)
430 ( 59)
I84( 94)
327(188)
767(201)
220 ( 64)
Vendor I)
210(119)
953(143)
1150(147)
257 ( 74)
573 ( 82)
820( 91)
887 (246)
477 ( 37)
SPENCE ET AL. ON VOLATILE ORGANIC COMPOUNDS
TAIII.I: .1—'Hie \f()C ahulKceonrenlraliomi measured itfter spikinn for the TCI.I'samples.
(areniKe of three with lilt' ilantlnril ili'vinlinn in iiureiilheses).
65
Compound
Acetone
1.2-IXT.
Chloroform
MI-K
TCI-
Dcn/enc
PF.RC
Chlorohcn/ene
Vendor A
148 ( 74)
457(127)
31 ( 1)
76.1 ( 29)
101 ( 6.1)
M 2) ,
2.13 ( 66)
48 ( 4)
Vendor I)
I80( 28)
313 ( 19)
29 ( 2)
198(128)
I80( 24)
6 ( 0.3)
197 ( 17)
38 ( 4)
Vendor C
I83( 24)
.10.1 ( 47)
27 ( 1)
210(262)
I83( 21)
4(0.4)
106 ( 21)
36 ( 4)
Vendor 1)
163 ( 26)
3f,3( 9)
27 ( 3)
637 (202)
10.1 ( 12)
8 ( 0.5)
I70( 36)
40 ( 3)
than while curing for 28 days inside the curing pipe. Although (he vapor VOC concentration
inside the curing pipe was significant, little mass was lost to the small headspace of these pipes.
The concentration retained in the cured grout was estimated from the concentration measured
in the spiked sludge correcting for the evaporation losses measured during mixing and curing
and for the dilution of the spiked sludge in the grout product. Table 4 lists the grout compo-
sition lor each vendor's product along with some other physical properties. The estimated
VOC concentration retained in the samples after curing and percent retention is listed in
Tables 5 and 6 for the static leach samples and the TCLP samples, respectively.
Static Li'iichiiiK
Figure I illustrates the scatter in the leaching data. Despite the scatter, the general trend in
Fig. I was obvious and was typical of this data. This trend was analyzed using the average
Icachatc concentration for all the samples at a given lime. The Icachatc for Vendor D's product
foamed during analysis, resulting in invalidation of much of the early data for in-house anal-
ysis until this problem was solved. As a consequence, only the single set of data for the sub-
mitted samples exist for this early time period for Vendor U.
TARLI: 4—Ci'iiiciiiili(in.\ waste farm composition uml physical properties.
Sludge-
Water added
Solid additives
l.illiml additives
Vendor A
COMPOSITION.
39.8
15.9
44. .1
<).()
Vendor D
WT%
9.1
IK. 5
6.1 .1
9.1
Vendor C
62.5
69
11.9
16.7
Vendor D
73.5
8.1
IK.4
0.0
I'HOHI-RTII-S
Density, kg/L
Volume increase. %
28-day uncoiil'med eonipressive
strength, kl'a
If.l
121.
6447.
1.62
784.
12 797.
1.22
91
83.
1.39
40.
414.
°Ufi as an unknown.
" This rcllecls the wl% of llie nnspiked sludge. The spike was uddcd as a water emulsion, hut this cxtrn
muss of water is included under "water nddcd."
-------
66 HAZARDOUS WASTES
TAIII.E 5—Ksiimateil I'()(.' cunciiiinilitm {nig/kgl retained in the cured cementitiims samples fir the
static hitch lexi. (The value in parentheses is the uV'ii aflhe I '<)(.' that was exliinaicd to he retained
llinnixli nii\inf! and curing.)
SPENCE ET AL. ON VOLATILE ORGANIC COMPOUNDS
ORNL OWC 90A-I367
67
Compound
Acetone
I.2-IXT-:
Chloroform
MUK
TCH
Rcnzcnc
PEKC
Clilorobcn/.enc
Vendor A
u
277 (67%)
.152 (76%)
83(73%)
226(81%)
270 (77%)
412(95%)
211 (95%)
Vendor 11
9 (75%)
8 (44%)
13(66%)
1 1 (76%)
1.1(64%)
12(67%)
.19 (72%)
50 (90%)
Vendor C
148(98%)
245 (75%)
I44(6K%)
286 (98%)
101 (81%)
174(79%)
510(98%)
122(82%)
Vendor!)
108 (6.1%)
482 (62%)
710(76%)
146(70%)
.192(84%)
480 (72%)
702 (97%)
.170 (95%)
' Lcfi :is .in unknown.
TCLP
Table 7 lists (he results of the TCLP test. (Table 7 lists only the VOCs thiit were spiked, but
(he oilier compounds were below their TCLP limits.) The extract Tor Vendor A did not exceed
any TCLP limits. The TCE limit was exceeded for Vendors B, C, and I), and the PP.KC limit
was exceeded for Vendor C. Referring to Tables I and 3. the spiked concentration exceeded
the site maximum concentration in ull cases, except for TCE for Vendors A and D. The ratio
of the site maximum to the spiked sludge concentration of TCP. for Vendor A was 1.29. Mul-
tiplying the TCE extract concentration for Vendor A by this factor yields 0.032 mg/L, still
below the limit of 0.07 mg/L. The equivalent factor for Vendors B anil C was 0.72, giving a
reduced ICE concentration of 0.051 mg/L (below the TCLP limit) for Vendor B and 0.22
mg/L (still above the TCLP limit) for Vendor C. A similar pro ruta reduction for PEKC and
Vendor C gave 0.06 mg/L compared to the limit of O.I mg/L. Thus, correcting the TCLP
extract concentrations by the ratio of the site maximum concentration to the measured sludge
concentration resulted in concentrations below the TCLP limits for Vendors A and B, but
TCE was still above the TCLP limit for Vendors C and D. Die ratio of the TCE limit to Un-
measured extract concentration was 0.23 and 0.37, respectively, for Vendors Cund D. Assum-
ing the extract concentration is proportional to the measured sludge concentration, the sludge
concentration would have to be lower than 43 mg/kg (33% of the site maximum) for Vendor
C and 38 mg/kg (29% of the site maximum) for Vendor D. The average of the TCI- concen-
trations measured for the samples taken from the buried lagoon during site charactcri/ation
i
o
o
<
a
UJ
rc
3
007
0.07
0 1
1.4
imil
...._
' No limil has been sel for this compound.
-------
68
HAZARDOUS WASTES
SPENCE ET AL. ON VOLATILE ORGANIC COMPOUNDS
69
pliilic clay could be targeted fur TCE (o improve performance; in Kiel, the cl:iy could he mod-
ified into two or more different forms to target different types of organic molecules. The per-
formance of such an approach needs to be studied and the economies compared to other
alternatives.
Analysis of Results
This section concerns estimation of the effective diffusion coefficients and distribution coef-
ficient from the static leach results. The static leach test involved leaching from the surfaces of
a slab. The initial concentration was assumed to be uniformly distributed in the slub and zero
for the leachalc. The leaching is assumed to be simple diffusion from the slab as defined by
Kick's second law, with the diffusion coefficient for the slab much less tlum the leachatc film
diffusion cocflicicnl. The Icachates were not replaced (static leaching), and, hence, leaching is
assumed to approach an equilibrium distribution of each specie between the slab and the
Icachate. Crank gives the following solution for this diffusion problem |.5|
I Alll.li K—NI\\\'II()X I'sliinuli'x nj thf IIKI.V.V traiix/iv iiamineu-rx (tin- lime delay for Vvmtor II ix #w';i
in imremhexis).
(/I,, - /«,) ; I
where the value represen-
tative of this ratio (say, 0.04) for the K values of /.ero in Table K, if it is desired to keep A math-
ematically correct as defined for this paper. For the purposes of this paper and considering the
Vendor
A
H( 17.6 days)
C
l>
A
11(1 6.7 days)
C
D
A
R( 18.8 days)
C
D
A
D( 12.2 days)
C
1)
A
11 (17.4 days)
C
L>
A
II ( 1 2.9 days)
C
D
A
II (12.8 days)
r
D
A
fl (0.5 days)
C'
1)
1). tin'/s
3.0 X 10 '
3.5 X K) '
ft
3.0 X 10 '
7.0 X 10 "
6.0 X 10 '
1.0 X 10 *
1.0 X 10 '
f
4.0 X 10 '
1.0 X 10 6
2.0 X 10 »
4.0 X 10 '
4.0 X 10 "
1.0 X 10' '
1.0 X 10 '»
2.0 X 10 "
1.3 X 10 '
5.0 X 10 '
1.5 X 10 '
7.0 X K) "
3.5 X 10 '
8.0 X 10 '
8.0 X 10 "
6.0 X 10 '"
2.0 X 10 »
1.0 X 10 4
4.0 X 10 lu
4.K X 10 *
1.0 X 10 *
6.0 X 10 "
1.8 X 10 '
/I/, mg /I,, nig
Afl'.TONI:
0.00" 5.0"
• 0.06 0.8
7.00 7.2
0.00" 16.0"
I,2-'|)ICIII.OROI:TIIF.NF.
10.0 24.0
0.00 0.7
4.00 12.0
13.0 36.0
OlLOROIORM
30.0J 306
0.00 I.I
0.70' 7.0
46.0 54.0
Ml!l IIYI RTIIYL KKTONI!
1.30 7.2
0.55 0.9
8.00 14.0
1.25 11.0
TR|< IILOROETNKNK
13.0 20.0
0.00 I.I
1.70 4.9
17.0 30.0
IlKN/KNP.
1 1.0 23.0
0.00 1 .0
1.40 8.5
14.0 36.0
Pi K( III OKOtTHKNK
33.50 36.0
0.00 3.4
22.0 25.0
51.50 53.0
16.50 20.0
0.90 4.3
0.00 5.9
21.00 28.0
l.cachuliilily
Index
6.5
7.5
.ft
6.5
7.2
7.2
6.0
7.0
f
7.4
6.0
7.7
6.4
7.4
8.0
6.0
7.7
7.9
6.3
7.8
7.2
7.5
6.1
7.0
9.2
8.7
9.0
9.4
8.3
9.0
7.2
8.7
K.
mg/l. grout
per mg/l.
water
0.0"
1.0
439.7
0.0"
9.0
0.0
6.3
7.1
628.IJ
0.0
1.4'
75.0
2.8
19.7
16.8
1.6
23.3
0.0
6.7
16.4
11.5
0.0
2.5
8.0
168.3
0.0
92.1
431.3
59.2
3.3
0.0
37.7
"The iiimmnl leaelied exceeded I he estimated .1,,; thus. .I/ WHS set as negligible and NI-WIIUX esti-
mated .-I,, and /). The low acetone concentration measured in the sludge used lu prepare Vendor A's
samples was suspected of lieing erroneous.
* This dnla set was pailieularly poor for evaluating I). Using all (he data. NI-WROX ;••' • -.'
I X 10 ', which is mil realistic, especially comliined with the higli K. This value is It-It ' -;. <
a more thorough analysis will hopefully give :i defensible value.
' NI-:WIK)X estimated ii suspiciously liiyli /) ol IX 10 " using llie gruphical estimate r-
-------
70
HAZARDOUS WASTES
SPENCE ET AL. ON VOLATILE ORGANIC COMPOUNDS
71
dala scatter, n value ofzero to u low units fur K means little or no significant interaction of the
specie with the solid body. A value of about II) probably means there wus significant interac-
tion with the solid body. The equivalent of the analytical solution is included in NF.WROX,
u computer program that estimates the least squares lit for up to live parameters for leaching
problems and that includes the equivalent lor several analytical solutions to Tick's second law
|r)|. In general, the average mass measured in the Icachale lor each vendor and specie at each
lime and the mass of each specie estimated retained in the slab (Table 5) were used as input to
NEWBOX to estimate two parameters, I) and .-I,. The distribution eocllicienl. K. was calcu-
lated from Ihis/l/und the mass estimated retained in thcsampleunereuring, /)„. One exception
to this approach was For the acetone in Vendor A's product. In this case A,, was left unknown
and estimated by NEWBOX, and /I, was assumed to be zero.
The trend for Vendor B's product wus to leach little or no mass for a few days, followed by
leach rules comparable lo the other vendors. This was not a simple diffusion process and could
not be handled by NEWBOX. The NEW BOX model wus modified for Vendor B by assuming
no leaching for a set time, followed by a simple diffusion, that is, a time olt'sel in Eq I. The
lime delay was estimated as the lime intercept of the least squares fit for the linearized form of
Ihcduta. The linearized form of the data comes from the much simpler solution of the diffu-
sion model for dynamic leaching of semi-infinite medium. From this solution, u plot of the
total amount leached versus the square root of time is linear. Finite gcomclricsand static leach-
ing will deviate significantly from linearity, but the early leaching behavior will mimic this
model. Thus, the quantity leached was plotted against the square root of lime, the linear por-
tion subjectively selected, and least squares analysis used on this portion to find the time inter-
cept for each specie. These lime delays were subtracted from the times for Vendor B's dala and
these corrected times used as input to NEWBOX to get estimates Tor I) and K. Table K lists
NEWBOX's estimates for D and K. as well as the teachability index defined tis
/, = - log(tf)
(3)
where
teachability index with 1) in cm'/s.
Discussion
The teachability index for these commercial products varied from 6.0 lo 9.4, and the distri-
bution coefficient varied from 0 to 62R. From past experience wild mobile species .such us
nitrate and some radionuclidcs, a teachability index of 6 to 7 is not very good for these waste
forms and indicates that unless a strong interaction exists Ihc specie will readily leach out of
the porous solid body (usually there is a correlation between the teachability index and the
distribution coefficient). Ccmcnlilious waste forms usually can achieve u teachability index of
7 to 8 and the belter ones can get us high as 9 or better for the more difficult species. Some
species arc more readily immobilized in ccmcnlitious waste forms, or arc just not very mobile,
and have a teachability index of 1 0 or higher.
Taking each specie individually, one would expect acetone to be quite difficult to control
because of its affinity for water, and this indeed proved to be the case. The teachability index
and distribution coefficient were low for thrcc(although Vendor B hud a fair teachability index
of 7.5) out of Ihc four vendors, but Vendor C's product never leached much of the acetone
estimated retained. The Icachale concentration stabilized ul u low level quickly, indicating
both a high interaction and low teachability index. (In fact, it stabilized so quickly that NF.W-
IIOX cstim^'' teachability index as 5. This seemed unreasonably low because water bus
a teachability index of about 5 and the distribution coefficient wus estimated so high.)
Although NI-WBOX estimates the (wo us independent parameters, I) and K ure expected lo
be related as follows
(4)
where
I),
•• true dilTusivily in the pore solution, cm'/s, and
• geometric factor, dimensionless.
This expectation raised questions about why Ihc acetone concentration stubili/cd at this low
value so quickly for Vendor C's product. Several explanations are possible, including: the
amount retained was in error and very little was actually in the sample; the original acetone
wus divided into two or more species, one of which wus "unlcuchublc" (strongly sorbed or
disappeared by reaction); and the concentration was actually slowly increasing but the ana-
lytical technique was unable lo detect this (the analytical variability has already been men-
tioned and acetone was one of Ihc harder compounds to follow at these concentrations). There
is not enough evidence at this time lo rule out or verify any of these explanations or other
possible explanations. All that is known is that little of the acetone estimated retained in the
Vendor C sample leached into the water according to analysis of the leachute.
For chloroform, although three of the teachability indices were still less than 8, Vendor D
hud u high K of 75 and Vendor A was even belter at 628. NEWBOX estimated the teachability
index ul 11 for Vendor A, quite high for ccmcntitious waste forms. This case was similar lo
the one for ucctunc with Vendor C in that not much leached. Considering the variability and
low concentrations, the index estimates for these two cases may be in considerable error.
The best performance for l,2-dichlorocthcnc wus observed for Vendor A's product with a
teachability index of 7.2 and a K of 9.0. Methyl ethyl kctonc, like acetone, has an ullinity for
water, but had a better performance than l,2-dichlorocthcnc with an index of 8 and u K of
16.8 for Vendor C. The best performance for trichloroelhcnc was for Vendor A with an index
of 7.7 and A' of 23.3. Vendor B had an index of 7.5 for benzene and a A'ofO, but Vendor A
had an index of 7.2 and a K of 11.5. The performance for pcrchloroclhenc and chlorobcn/.ene
wus belter than for the other compounds, tip to 9.4 and 9.0, respectively, for the index and 431
and 59 for K
Conclusions
The TCLP was judged not satisfactory for testing the immobilization potential of ccmcn-
litious waste forms. Consequently, the immobilization potential was tested by static leaching
and subsequent estimation of Ihc teachability index and distribution coefficient.
Although open mechanical mixers were required lo mix the sludge and treatment solids, the
resulting reactions were exothermic, and Ihc products were cured for 28 days; most of the
VOCs were retained in the cured samples. The large uncertainty in VOC analysis means
Ihc error bars were large lor the parumclcrcslimulion. The estimated error for Icachale unalysis
wus from 5 to 15%, depending on the compound, but the error in the parameter estimation
wus ulso affected by the errors in spiking and subsequent sludge analysis. Purl of Ihc problem
was the inability of I lie standard extraction technique to extract some compounds completely
from the sludge for analysis. As a consequence, the VOCs tended lo be underestimated in the
sludge and the subsequent testing and parameter estimation tended lo be conservative because
more VOCs were actually present in the samples than estimated. It is not unusualr Mic teach-
ability index lo vary by 0.2 without such large analytical errors. The leacliabil' i range
-------
72 HAZARDOUS WASTES
for (his sluily may be 1.0 or mure, with the reported estimates at the low end, and the estimates
for K should probably be considered order of magnitude estimates.
Strong interactions were estimated lor acetone, chloroform, and perchloroelhcne and sig-
nificant interactions for 1,2-dichloroethcnc. methyl ethyl kelonu, triehloroethcne, hen/one,
and chlorobcn/.enc. but no single product appears to interact significantly for all eight com-
pounds. This implies that it is possible for the vendors to formulate for a combination of VOCs
using a mixture of additives unless the different additives used by the vendors interfere with
each other. Despite the evidence of interaction, the estimated leuchabilily indices were dis-
appointingly low except Tor perchloroelhcne and chlorohen/cnc. It is possible that some, hut
not all, of a given VOC was strongly sorbcd and that the "free" VOCs quickly leached out,
giving a relatively low index but a high or moderate K. Nevertheless, these low or moderate
indices agree with the observation that the sludge concentration must he limited ul about the
spiked levels or less (< 1000 mg/kg) to pass the TCLP test. The TCI.P results proved that a
commercially available ccmcntitious waste form can puss the TCLP criteria for sludge con-
centrations indicative of this site. Based on these results, stabilization/solidification is a viable
alternative for a sludge or soil that is heavily contaminated with metals and lightly contami-
nated with VOCs. In such a case, incineration is an expensive alternative that will likely con-
vert the metals into a more mobile form requiring further treatment of the incinerated sludge/
soil. Currently available additives proved capable of handling VOCs with limited success,
albeit good enough to pass TCLP for this site. Perhaps belter additives will be developed (hat
will handle even higher organic concentrations if S/S is accepted for such applications.
/tcliiiowletlgmem
This research was sponsored by the Office of Defense Waste and Transportation Manage-
ment, Defense Programs, U.S. Department oflincrgy, undcrConlracl DE-AC05-840R2I400.
References
| /) "Stabilization/Solidification of CERCLA and RCRA Wnslcs. Physical Tests. Chemical Testing Pro-
ccdurcs. Technology Screening, and Field Activities." EPA/625/6-89/002. Center for Environmental
Research Information and Risk Reduction Engineering Laboratory, U.S. Environmental Protection
Agency, Cincinnati, OH, May 1989.
|,?| Weilzmun, I.., Hanicl, L. li., and Danh, E., "I-valuation of Solidilicalion/Slahili/alionasa Hcsi Dem-
onstrated Available Technology," 14th Annual Hazardous Waste Engineering laboratory Confer-
ence. Cincinnati, OH. May I9K8.
| J] Gibbons, J. J. and Soundararajan, R.. A/mriiwi Luhiirultiry, Vol. 20, No. 2, I9HK. pp. .1H-46.
\4\ "Prohibition on the Disposal of Bulk Liquid Hazardous Waste in Lundlills—Statutory Interpretive
Guidance," OSWER Policy Directive No. 9487.002A, EPA/5.10-SW-OI6, U.S. Environmental Pro-
tection Agency, Cincinnati, OH, June 1986.
|.J] Crank, J., 'rlH'MullH'iiitilirxiifDiJJiixiiin. Oxford University Press, London. 1956, pp. 52-56.
jo] Nestor, C. W., Jr., Godbcc. II. W.. and Joy. D. S., NIMIIOX. A Gun/m/rr Gu/c/iir 1'iirniwH'r Kai-
iimliwi in DiJl'm-iiin I'mhlrim. ORNI./TM-10910, Oak Ridge National Laboratory. Oak Ridge. IN
(in preparation).
Nancy J. Sell.1 Mark A. Revall.2 William llenllcy.* and
Thomas 11. Mclnlosh*
Solidification and Stabilization of Phenol and
Chlorinated Phenol Contaminated Soils
RITICRKNCK: Sell. N. J.. Revall. M. A.. Dcntley, W.. and Mclnlosh. I. II.. "Solidification and
Slulilll/atinii of Phenol and Chlorinated I'livnol Conlaminalcd Soils," Slul>ili:(ilii>» unit \iilidi-
lii'tiliiiii ill llii-iirilnii\. KmliiiMlm: mill Mixed II•ru/i'.v. 2nd 1'Wn/nc. AS'I'M S'l'l' II2J, 'I'. M.
Ciilliain andC. C'. Wiles. Eds., American Society for Testing and Materials, Philadelphia. 1992,
pp. 73-K5.
AIIS'IR ACT: Phenol and chlorinated phenols are toxic compounds found in many treated wood
products such as fence posts ami railroad lies, hence .soils near such treatment facilities or near
old railroad yards can be quite contaminated. This study investigated the results of using sodium
bentoniteclay modified with dimethyl ditliydrogcnatcd tallow) ammonium chloride mixed with
Type I portland cement to immobilize a series of phenols (phenol, 2,4,6-trichlorophcnol. and
nciuachloroplicnol) from a sandy Shawano II liori/on (lypic Udipsamment) soil.
The lest soil was mixed with the various phenols at a contaminant concentration of 1001) nig/
kg. An admixture of contaminated soil and modified clay (0 to 10% w/w organoclay) was pre-
pared, lina! solidification was done by adding cement at concentrations of 16 to 39% w/w. fox-
icily characteristic leaching procedure (TCI.P) and unconlined comprcssivc strength determi-
nations were made. The results of these tests indicate potential for using these organoclay
admixtures for treating soils contaminated with various chlorinated phenols.
KKY WORDS: organoclay, phenols, chlorinated phenols, stabilization, solidification, site reme-
diation, toxic wastes
Unintentional conlaoii nation of soil with toxic chemicals is a continuing problem. The U.S.
General Accounting Office estimates that as many as half of the 5000 ha/ardotis waste sites
regulated by the U.S. Environmental Protection Agency (EPA) may be leaking ha/ardous
materials into local carlh materials and then to groundwutcr | / ].
Many of these toxic chemicals arc organic in nature, some with potentially severe adverse
effects. They can be carcinogenic or mulagcnic or both in man and animals, toxic to aquatic
life, and generally degrade the quality of water for human consumption. Hence, there is a need
to develop new and alternate control technologies capable of preventing these toxic chemicals
from dispersing through soil into aquifers.
A variety of different siahili/ation and solidification technologies have been developed in
recent years 12\. Suggestion has hecn made thai site remediation can be accomplished by using
an organically modified clay (organoclay) | (| This study focuses on the possibility of using an
organoclay to slabili/e phenol and chlorinated phenols in contaminated soils. |
To he feasible for slabili/ingiuul solidifying contaminants, a treatment procedure must pro-
duce a waste that (I) withstands a pressure old..144 MPa (50 psi) when applied in un uncon-
' Professor, research assistant, and professor, respectively. University ul Wisconsin—Green May. 2420
Nicolcl Drive. Cireen Day. Wl 54.111-7(101.
1 Vice-president, Research and Development. J. V. Manufacturing Co., P.O. llox SV> ' j.
54115.
73
-------
CD
D
Q.
x'
X
-------
Appendix XI
Army Waste Classification Guidance for Building
Demolition Debris Containing Lead Based Paint
-------
01 Off
WASTE CLASSIFICATION GUIDANCE
FOR BUILDING DEMOLITION DEBRIS
CONTAINING LEAD BASED PAINT
PURPOSE; This guidance provides two different acceptable
methods for the characterization of the solid waste generated
during demolition operations through sampling and Toxicity
Characteristic Leaching Procedure (TCLP) analyses. Using either
method, demolition debris can be characterized as hazardous or
non-hazardous waste as defined by RCRA. These methods apply to
demolition debris only and do not apply to heavy metal bearing
wastestreams that are generated from other specific operations
(e.g., paint scrapings, sandblast residues, etc.)* Throughout
this document, lead contamination, the most common TCLP debris
concern, is used as an example, although these methods can be
used to classify other TCLP wastes as well.
KETHODS; Method I- The Sampling/Statistical Analyse* Method
requires sampling and TCLP analyses of both the paint and
building material. The data is analyzed using conventional
statistical methods to transform the results to a confidence
interval (CI) of 80%. Method II- The Mass Balance TCLP Method
requires only sampling and TCLP analyses of the paint and adjusts
the TCLP data by a factor based the calculated uncontaminated
mass in the total debris.
Method I. Sampling/Statistical Analyses;
SCOPE:
a. Before characterizing the waste, it is necessary to define
the wastestream. The wastestream is the debris generated during
a given demolition project at a given site/installation. While
all buildings/structures generating demolition debris constitute
the wastestream, only a percentage of these buildings need be
sampled. Details on how to determine the appropriate number of
buildings to sample are presented in the "PROCEDURE" section
below.
PROCEDURE; During demolition debris waste characterization,
several site-specific determinations need to be made. The
following steps explain how:
a. Defining Individual Wastestreams/Populations; As
defined above, the wastestream consists of all the debris
generated during a specified demolition project. A list of the
buildings should be recorded, including the building components
undergoing demolition , and notations of buildings that will be
generating the same type of debris because they are the same or
similar design and construction and are undergoing the same type
of demolition or rehabilitation. Information should also be
gathered regarding the demolition and disposal procedures.
-------
For instance, if the structures are set on cement foundations it
would be necessary to determine whether the cement is to be
demolished and disposed of with the rest of the debris. If such
foundations were to be left in place they would not be considered
as debris; otherwise, they would be included in the wastestream
and would be sampled in accordance with the procedures discussed •»
below.
b. Determining the flmnfe^r of Samples; Based on
EPA guidance (EPA/600/8-89/046, March 1989, Soil Sampling Quality
Assurance User's Guide, 2nd Edition), a statistical approach will
be used to determine the number of buildings that need to be
sampled. This approach is based on the assumption that the
buildings are all relatively uniform and that the analytical
results of the study will be normally distributed. The EPA
manual SW-846 — Test Methods for Evaluating Solid Wastes, Section
9.1.1.3, Basic Sampling Strategies (Attachment A) , requires that
the number of samples used to characterize a wastestream ensure
an 80 percent confidence level in the resulting determination (in
this case, hazardous or nonhazardous waste determination) . The
enclosed Table 1 is based on these guidelines and should be used
to determine the number of buildings to be sampled at a given
project site.
c. Sample Buildings Selection; Once the number of
buildings to be sampled has been determined, the specific
buildings to be sampled need to be identified. For buildings
generating identical or similar debris (made t I the .ame
construction materials and painted with the same paint) a random
approach should be used in the selection process. Buildings may
be randomly selected using building numbers or placement on maps.
However, when one or more groups of buildings generating :
identical or similar debris constitutes a separate and distinct
segment within the total number of buildings, an appropriate
percentage of buildings should be selected from the individual
group (s) .
d. Sampling Strategy; The objective is to obtain one
representative composite sample from the debris wastestream from
each building selected for sampling. The composite sample must
include appropriate proportions of each debris that the
wastestream is made of. Figure 1 depicts various areas of a
building that may be constructed of different materials and must
be sampled if they are part of the debris wastestream. Areas
that will not be part of the debris wastestream do not have to be
sampled.
-------
(1) Debris components, such as glass, screen,
or wiring, that are difficult to sample and comprise a very small
(de minimis) percentage of the debris vastestream, do not have to
be sampled. Also materials such as aluminum siding,, large metal
ductwork, light ballasts, utility equipment, and asbestos
insulation need not be sampled if these materials are separated
from the demolition debris and recycled/reused (e.g., scrap
metal). In general, the most commonly sampled components will be
wood, brick, cement and plaster/wallboard.
TABLE 1- STATISTICAL DETERMINATION OF THE NUMBER OF BUILDINGS TO
BE SAMPLED
NO. OF TOTAL BUILDINGS
AT ONE PROJECT SITE
NO. OF BUILDINGS TO SAMPLE*
1-9
11 - 15
16 - 20
21 - 30
31 - 40
41 - 100
> 100
ALL
10
13
16
21
26
32
* It should be noted that a sample is defined as a composite of
subsamples from one building. 20-30 subsamples should be
sufficient to make one sample.
2) The proportional size of the various building
debris components based on (estimated) square footage oust be
determined. For instance, a building may be 70 feet long, 40
feet wide and 12 feet high; if all four of the exterior walls are
to be demolished and are made of the same material, there is 2640
ft2 of that debris component. Window and door space should be
subtracted out from the exterior-interior walls and considered as
separate debris components. The estimated area of each debris
component (e.g., exterior wall, interior plaster board wall,
interior plywood/panelling wall, floor, cinder block supports,
-------
etc.) should be compared to one another in order to establish
ratios. The ratios will determine the number of subsamples to
obtain from each individual component. For instance, if 20% of
the area is cinder block, than 20% of the subsamples should
consist of cinder block camples.
Generally, 20 to 30 subsamples are necessary to make-up one no-
gran composite sample for each building. This number will vary
based on the number of components that make up the debris. For
instance, if building demolition debris consists of 60% vails,
30% floor and 10% doors (based on surface area), 18 subsamples
(60/100 x 30) could appropriately be from the walls, 9 from the
floor and 3 from the doors.
e. Sampling Methodology;
(1) Using a 1-inch bit drill or similar device,
"core" subsamples should be obtained from each component of the
building demolition debris. The number of subsamples taken for
each debris component relative to the other debris components
will be based on the ratios calculated above. The subsamples
should be collected into a disposable container (such as large
sheets of paper) as the drilling is done. The sampling crew
should — to the extent possible -*- drill through the entire
thickness of each component (e.g., doors, floor, etc). For
building debris components such as cinder block or cement, a
hammer drill should be used. The number of drill holes obtaine^
from each component should be recorded. If the amount of
material collected for the total composite sample for the
building is not enough (i.e., less than 110 grams) for the TCLP,
additional subsamples should be obtained from each of the
specific components, with the number of additional subsamples
based on the above calculated ratios. [NOTE: For at least 5
percent of the samples (and a minimum of 1 sample) taken for each
demolition project approximately 300 grams should be obtained for
adequate split laboratory analyses.]
•
(2) Field duplicates, equaling 5 percent of the number
of actual composite samples (at a minimum of one), taken after
each demolition project, should be obtained to check the sampling
practice. The duplicate(s) should be obtained by simultaneously
filling two sample containers during the sample process (i.e.,
for each subsample within a sample building, two adjacent cores
should be obtained and placed into two separate containers).
f. Collection and Labelling; The sample material from each
building debris should be collected onto a (disposable) container
(such as sheets of unused paper, paper plates, etc.). From this
collection container, the materials should be emptied into clean
(new) plastic baggies and labelled with the project/installation
name and or identification number, sample (building) number,
sample date, and sampling personnel's name.
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g. Decontaminationr Kondedicated sampling equipment
such as the drill bit should be decontaminated between sampling
of individual buildings. The sampling crew should first brush
excess material from the equipment and then wash using tap water
and soap. This should be followed by a final rinse with
distilled, deionized, filtered (DDIF) water. To ensure the
equipment was properly decontaminated, a used rinse water sample
should be taken and analyzed.
LABORATORY ANALYSES;
a. Packaging and Transportation; All samples should be
properly packaged before transporting them to the certified
analytical laboratory.
b. Laboratory Preparation; To ensure thorough mixing of
the composite sample, the laboratory should be requested to
thoroughly mix/homogenize the sample before preparing it for
analyses. This will minimize the "settling11 that may occur
during transportation. This procedure is extremely important
when excess sample has been obtained and the laboratory will only
be using a portion of the overall sample.
c. Analytical Methodology; All solid material being analyzed
(wood/plaster/paintchip, etc.) should be extracted using EPA
Method 1311 (TCLP). The samples should be analyzed using either
EPA Method 6010A [Inductively Coupled Plasma (ICP;-Atomic
Emission Spectroscopy] or EPA Method 7421, the Atomic Absorption-,
Furnace Technique for lead. The ICP procedure is recommended due
to lower cost, but either method will satisfy EPA requirements.
The rinsate sample should also be analyzed using one of these
methods.
DATA ANALYSES;
\
a. The TCLP laboratory results should be statistically
analyzed to assess the variability among the buildings of the
demolition or rehabilitation project and overall normality of the
TCLP lead concentration distribution. If the analytical results
do not indicate a normal distribution (i.e., the arithmetic mean
is not greater than the variance), the raw data should be
transformed. After normality has been achieved through an
appropriate transformation, the 80 percent confidence interval
(CI) should be calculated and compared to the (similarly
transformed) regulatory threshold (RT) of 5.0 mg/L for lead. (See
SW-846—Test Methods for Evaluating Solid Wastes, Section
9.1.1.3, ffasie Sampling Strategies).
-------
b. Additional procedures may be necessary to address
potential "statistical outliers," or buildings that yield
unusually high TCLP lead concentrations that dramatically skew
the 80 percent CI. If necessary, such buildings may be addressed
as a separate population. " .'
An example of a sampling/data analyses program is attached below
(Example 1.0). See Test Methods for Evaluating Solid Waste, EPA
Manual SW-846, Vol. II, Chapter 9, November 1986 (Attachment A)
for detailed calculations. *
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EXAMPLE 1.0
STATISTICAL ANALYSES
Building Debris Samples: Collected Mav-June 1992
Bldg
4711
4900
4901
4905
4713
3644
3626
3635
3641
3628
3639
3640
3629
3632
3637
3627
4904
3634
Pb Values
(ng/L)
1.08
1.11
14.7
10.0
1.35
3.11
1.40
1.63
1.53
1.76
1.38
0.50
0.51
1.06
0.91
0.82
2.56
0.50
square root of Pb values
1.039
' 1.054
3.834
3.162
1.162
1.764
1.183
1.277
1.237
1.327
1.175
0.707
0.716
1.030
0.952
0.907
1.600
0.707
mean
std deviation
std err
normal
80% CI*
trsfd RT
Hazardous
waste
2.55
3.61
0.85
No
N/A
N/A
N/A
1.38
0.80
0.19
Yes
1.63
2.24
NO
*80% Confidence
Interval «= mean
(tjo*std err) ; w
tapl.333 for df
+
here
=17
By performing a square root transformation
of the values, the data shows a NORMAL
distribution (the mean > the STD squared).
Since the 80% CI is LESS than the square root of the
regulatory level -of lead (5 mg/1) the waste is not
hazardous.
Reference: Test Methods for Evaluating
Solid Waste, EPA Manual SW-846, Vol. II,
Chapter 9, November 1986. (Attachment A)
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8
Method II. VftBfl p^IAKCE TCLP CALCULATION METHOD;
SCOPE:
a. This method is based on the assumption that for building
demolition debris, only the paint will contain heavy metals
(e.g., lead) while the unpainted building construction materials
will contain no heavy metals. In this instance, TCLP sampling
and analyses of only the paint is required. If the above
assumption is not valid, then the* Sampling/Statistical Analyses
Method (Method I) must be used.
b. Before characterizing the waste, it is necessary to define the
wastestream. The wastestream is the debris generated during a given
demolition project at a given site/installation. While debris from all
buildings/structures being demolished or rehabilitated constitute the
vastestream, only a percentage of these buildings need be sampled.
Details on how to determine the appropriate number of buildings to
sample are presented in the "PROCEDURE" section below.
PROCEDURE: During a demolition debris waste characterization study,
several site-specific determinations will need to be made. The
following steps are detailed to the extent possible.
a. Defining Individual Wastestreans/Populations; As
defined above, the wastestream consists of all the debris generated
during a specified demolition project. A list of i:*ue buildings should
be recorded, including the building components undergoing demolition,
and notations of buildings that will be generating the same type of
debris because they are the same or similar design and construction and
are undergoing the same type of demolition or rehabilitation.
Information should also be gathered regarding the demolition and
disposal procedures.
For instance, if the structures are set on cement foundations it would
be necessary to determine whether the cement is to be demolished and
disposed of with the rest of the debris. If such foundations were to
be left in place they would not be considered as debris; otherwise,
they would be included in the wastestream and would be sampled in
accordance with the procedures discussed below.
b. Determining th^ number of Samples; Based on EPA guidance
(EPA/600/8-89/046, March 1989, Soil Sampling Quality Assurance User's
Guide, 2nd Edition), a statistical approach will be used to determine
the number of buildings that need to be campled. This approach is
based on the assumption that the buildings are all of a relatively
uniform construction and that the analytical results of the study will
be normally distributed.
-------
The EPA manual SW-846—Test Methods for Evaluating Solid Wastes,
Section 9.1.1.3, Basic Sampling Strategies (Attachment A), requires
that the number of samples used to characterize a vastestream ensure a
80 percent confidence level in the resulting determination (in this
case, hazardous or nonhazardous waste determination).' Table 1 (Method
1} is based on these guidelines and should be used to determine the
number of buildings to be sampled.
c. Sample Buildings Selection; Once the number of
buildings to be sampled has been*determined, the specific buildings to
be sampled need to be identified. For buildings generating identical
or similar debris (made of the same construction materials and painted
with the same paint) a random approach should be used in the selection
process. Buildings may be randomly selected using building numbers or
placement on maps. However, when one or more groups of buildings
generating identical or similar debris constitutes a separate and
distinct segment within the total number of buildings, an appropriate
percentage of buildings should be selected from the individual
group(s).
d. Sampling Strategyt The objective is to obtain one
composite sample of paint from each building selected for sampling.
Only samples of paint from the building components that will be part of
the debris vastestream should be sampled.
e. Sampling Methodology;
(1) Using a scraper or similar device, paint samples should be
r**taine^ from each component of the demolition debris. Typically, one
should sample each component of the debris that contains lead paint and
combine the samples into one composite sample (Jcnowing that at least a
100-nog composite sample is needed for a TCLP analyses and that at
least a 10-15g sample must be obtained from each debris component).
The choice of and number of samples should be approximately in
proportion to the areas of each building component that has been
painted with the lead paint and that will make up the debris
wastestream. Table 2 below provides an example of the percentage of
total building debris area that each debris component comprises and the
number of grab samples that should be taken of each component. Again,
if any of these building components will not be part of the debris
wastestream, they should not be sampled. [NOTE: For at least 5
percent of the samples (and a minimum of 1 sample) taken for each
demolition project approximately 300 grams should be obtained for
adequate split laboratory analyses.]
-------
10
TABLE 2- PERCENTAGES OF AREAS COVERED BY LEAD PAINT
Category
Area
Percentage
of Subsamoles
Interior
Ceiling
Halls
Doors
Windows
Cabinets
Shelves
519.6
1137
352.4
132
46
55
13%
28.4
8.9
5.8
>
• _'
3
6
2
1
1
1
Exterior
Siding, Attic 201.6
Siding, Halls 1000
Roof, Underside 200
Porch 355.5
5.0
25.0
5.0
Totals
3999.1
100.0%
1
5
1
23
(2) Field duplicates, equaling 5 percent of the number
of actual composite samples (at a minimum of one), taken during each
demolition project, should be obtained to check the sampling practice
The duplicate (s) should be obtained by simultaneously filling two .
sample containers during the sample process (i.e., for each sample
within a sample building, an adjacent grab sample should be obtained
and placer* into « separate container).
f. Collection and Labelling; The sample material from
each building debris should be collected onto a (disposable) container
(such as sheets of unused paper, paper plates, etc.). From this
collection container, the materials should be emptied into clean (new)
plastic baggies and labelled with the project/installation name and or
identification number, sample (building) number, sample date, and
sampling personnel's name. .
g. Decontamination; Nondedicated sampling equipment
such as the drill bit should be decontaminated between sampling of
individual buildings. The sampling crew should first brush excess
material from the equipment and then wash using tap water and soap.
This should be followed by a final rinse with distilled, deionized,
filtered (DDIF) water. To ensure the equipment was properly
decontaminated, a used rinse water sample should be taken and analyzed.
-------
11
LABORATORY ANALYSES t
a. Packaging and Transportation; All samples should be
properly packaged before transporting then to the certified analytical
laboratory.
b. Laboratory Preparation t To ensure thorough nixing of
the composite sample, the laboratory should be requested to thoroughly
mix/homogenize the sample before preparing it for analyses. This will
minimize the "settling" that may'occur during transportation. This
procedure is extremely important when excess sample has been obtained
and the laboratory will only be using a portion of the overall sample.
c. Analytical Mcthodoloo^r; All paint being analyzed
should be extracted using EPA Method 1311 (TCLP). The samples should
be analyzed using either EPA Method 6010A [Inductively Coupled Plasma
(ICP) -Atomic Emission Spectroscopy] or EPA Method 7421, the Atomic
Absorption, Furnace Technique for lead. The ICP procedure is
recommended due to lover cost, but either method will satisfy EPA
requirements. The rinsate sample should also be analyzed using one of
these methods.
DATA ANALYSES;
I) TCLP DATA ANALYSES;
a. If only one bui .ding **s sampled (e.g., the same paint was used in
the other buildings) no statistical analyses need be performed oh.the
TCLP data. If more than one building was sampled the TCLP laboratory
results should be statistically analyzed to assess the variability
among the buildings of the demolition project and overall normality of
the TCLP lead concentration distribution. If the analytical results do
not indicate a normal distribution (i.e., the arithmetic mean is not
greater than the variance), the raw data should be transformed. After
normality has been achieved through an appropriate transformation, the
80 percent confidence interval (CI) should be calculated.
b. Additional procedures nay be necessary to address
potential "statistical outliers," or buildings that yield unusually
high TCLP lead concentrations that dramatically skew the 80 percent CI.
If necessary, such buildings may be addressed as a separate
wastes tream.
-------
12
II) TOTAL WASTESTREAM TCLP DETERMINATION;
After obtaining statistically acceptable TCLP of the paint from step I,
above (where only one building had to be sampled, the TCLP value for
the one composite sample is used), the TCLP level of the total debris
wastestream can then be estimated from a TCLP sample. The key
relationship can be derived as follows:
TCLPwaste = TCLPpaint at mp / mw,
Where mp is the mass of the paint on the building surfaces,
and mw is the total mass of the debris wastestream generated.
This simple proportion will provide a reasonable estimate of
the TCLP for the debris wastestream which can be directly
compared to the regulatory standard (e.g., 5.0 mg/1 for
lead).
a. Estimation of the Mass of Paint and Total Wastes:
Two basic formulas will be defined to estimate the parameters, mp and
DV:
np(kg) = Ap(ft2) x dp (ft) x rp(g/cc) x 28.3 (kg/ft3)
where Ap is the surface area of paint; dp is the depth of the paint
surface; and rp is the paint density and 28.3 (kg/ft*) is the density
of water.
ow(kg) «= Vi(ft3) x ri(g/cc) x 28.3 (kg/ft3)
where i are the various debris components, such as wood, concrete,
brick, etc, Vi is the volume and ri is the .density of each debris
component. The mass of each of the separate components are estimated
using standard construction estimation techniques.
Estimation values for the densities of materials and the depth of the
paint surface can be obtained from many sources. The density values
given below are from "The Handbook of Chemistry and Physics" and the
experience of the agency. Estimated average paint depth was obtained
from the Denver Housing Authority.
-------
13
Estimated values for ri, rp and dp:
Density of Concrete
Density of Wood
Density of Glass
Density of Steel
Density of Plaster
Density of Gypsum Board
Density of Brick
Density of Stone (typical)
Density of Soil (dry)
Density of Pipe
Density of.Paint
Average Paint depth
2.5 g/cc
.6 - .8 «
2.5 •
7.5
1.5
.8
2.0
2.5 '
1.4
7-8
1.2
1/100 inch
(8.33 X 10-* ft)
The paint depth value is considered reasonably representative, but if
the TCLP sample contains abraded material (such as wood or plaster),
the average depth should be measured on-site and the mass of paint plus
abraded material calculated.
The estimation of the volume of waste materials and the area covered by
the paint surface will take the greatest amount of time. As an example
of how this can be done, a typical one story house design was created
for calculation purposes (Table 3). Where a number of similar
buildings are involved, a single "representative" building could be
used. If architectural drawings happen to be available, much of the
information can be obtained directly from them.
Lead-painted surfaces are assumed to include all interior walls and
ceilings as well as interior trim, windows, doors and kitchen cabinets.
It is also assumed that the outside walls of the house and porch were
painted with lead based paint.
Many of the volumes for the foundation, framing, and plaster surfaces
can be estimated from geometric properties. Density values and the
specific weight of water in kg/ft3 are multiplied by the volume to
obtain the weights for each material. The complexity due to the number
of items involved is characteristic of residential housing. Federal
installation buildings may be somewhat simpler.
Table 3 summarizes the calculation results for the basic structural
categories. Area calculations are provided only where it is assumed
that lead based paints were applied. The total estimated weight of the
house and associated materials was 72,173 kg, which constitutes the
debris wastestream. The total painted interior surface area was 2242
ft2; the outer painted surfaces totalled 1757.1 ft3. It was assumed
that the paint thickness was .01" on average. The estimated weight of
paint was 113.1 kg, the total mass of sample containing lead.
-------
14
TABLE 3. HOUSE ESTIMATION VALUES BY CATEGORY
Category Volume fft3) Density Factors Weight
Estimate of Total Debris Mass
•%
Concrete 648.5 X 2.5 x 28.3 «= 45,881 kg
Brick Chimney 59.1 x 2.0 x 28.3 « 3,345
Wood, Framing 653.8 x .7 x 28.3 « 12,952
Asphalt Roofing 26.0 ' x 1.5 x 28.3 «= 1,104
Steel, Glass, Appliances 1,466
Soil & debris 100 x 1.4 x 28.3 - 3,962
Plaster/Lath . 86.3 x 1.5 x 28.3 « 3.663
Sum 72,372 kg
Estimate of Paint Areas and Mass:
Interior Area fft2!
Ceiling 519.6
Walls 1137
Doors 352.4
Windows 132
Cabinets 46
Shelves £5
Totals 2242
paint weight (kg) = paint area (ft2) x paint depth x paint density
= 1.868 ft3 X 1.2 X 28.3 = 63.4 kg
Exterior Area fft2)
Siding, Attic 201.6
Siding, Walls 1000
Roof, Underside 200
Porch 355.5
Totals 1757.1
- 1.464 X 1.2 X 28.3 "= 49.7 kg
Sum of all building paint «= interior + exterior paint mass «=
63.4kg + 49.7kg « 113.1 kg
The ratio of masses, mp/mw - 113.1/72373 «= 1.56 X 10*3. This means that
for a value of 5 mg/1 TCLP to be equalled or exceeded in the debris a
corresponding TCLP value of: 5/1.56 x 10"3, or 3200 mg/1 Pb, would have
to be obtained in the paint sample.
-------
Figurt i
Example Diagram of a Bunding
Ttmponry Barracks Slattd for Dtmofition)
Insldo: Panhlon Wans
CtSBng
Imar Structurt: *€tudi*
Support Btams
HOOF
D
WINDOW
FRAMES
D D D
SAS&FOUNOAT10N
BOOKS
-------
•o
CD
D
Q.
-------
Appendix XII
1992 Workshop on Characterizing Heterogeneous
Materials
-------
r^EPA
United States
Environmental Protection
'Agency
Office of Research and
Development
Washington, DC 20460
EPA/600/R-93/033
March 1993
Environmental Monitoring
Issues
Results of Workshops
Held in July 1992 as
Part of EPA's Eighth
Annual Waste Testing and
Quality Assurance Symposium
-------
5. CHARACTERIZING HETEROGENEOUS MATERIALS
5.1. BACKGROUND
In both the RCRA and CERCLA programs, a material often must be characterized to
determine if it possesses some property of concern or interest. Types of questions that may
require answering include:
• Is the material hazardous?
• "Can it be safely or successfully managed using a specified treatment technique?
• How much supplemental fuel must be added to incinerate the waste?
When the material being characterized is homogeneous, conventional sampling and
subdividing approaches can be employed. For example, in a truckload of used foundry sand
with an average phenol concentration of interest, the material is in the form of relatively fine
particles with the phenol uniformly distributed on the surface. Conventional compositing and
subsampling can provide representative samples with an average composition very close to that
of the entire load. The actual task of obtaining each subsample from the appropriate point in
the truck may be very difficult, but the approach used is relatively straightforward.
However, insurmountable problems can develop when faced with a heterogeneous
material. Heterogeneity is a relative term and, among other factors, is a function of the
objectives of the characterization and the analytical sample size. This workshop was concerned
with wastes of such various particle size, waste consistency, or extraordinary concentration
gradients that the sampling and analytical objectives could not be met using traditional
approaches and standard techniques. This is an important and difficult problem that has been
of concern to many organizations involved in waste management.
38
-------
The workshop goal was to advance the state-of-the-art techniques for characterizing
difficult to sample wastes. This covers wastes with a highly variable nature, (e.g. wide ranges
of particle size, large concentration gradients, and mixtures of different waste materials (e.g.
dredge materials containing sludge, tires, construction debris, bottles, cans, etc.)). These types
of materials present challenges that traditional sampling and analysis approaches cannot meet
with the level of certainty required for modem waste management decisions.
RCRA has historically taken the position that the sample actually being analyzed does not
have to be representative of the material being characterized, but rather that the sum total of the
data must represent the property of interest. The problem presented was how to develop
practical solutions to characterize these difficult situations. In this session, the participants
discussed how to cost-effectively characterize materials that are inherently very heterogeneous
and present characterization difficulties.
5.2. SUMMARY OF POSITION STATEMENTS
5.2.1. Regulatory Program Perspective
Mr. Charles Ramsey, EPA's National Enforcement Investigation Center (NEIC),
reviewed some issues involved in implementing the RCRA regulatory requirement that a
"representative" sample of the waste be collected and analyzed. 40 CFR, Part 260.10 stipulates
that a representative sample, '... means a sample of a universe or whole (e.g., waste pile,
lagoon, ground water) which can be expected to exhibit the average properties of the universe
or whole." This definition has two aspects.
1. What is an average property?
2. How is the universe or whole defined?
The inability to answer these questions in clearly defined scientific terms leads to most of the
problems surrounding the characterization of heterogeneous wastes.
39
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Mr. Ramsey Proposed that hazardous waste characteristics are not "averageabi
properties. For example, corrosivity is expressed as pH that is a logrithemic function, while.
ignitibility can be expressed as passing or failing the 60°C ignition test. With these
characteristics, the numerical mean is not meaningful; therefore, an average value cannot be
obtained.
Using the average value as a measure of hazard with respect to the toxicity and reactivity
characteristics may also present potential problems. When the material to be evaluated consists
of both a contaminated phase and an inert phase, use of the mean may result in a waste being
classified as nonhazardous even though a substantial portion of the waste might be above the
regulatory threshold and pose an environmental hazard.
Using "the most likely result" approach (also known as attribute testing) avoids many of
the above problems. It requires that a certain percentage (e.g., 50%, 75%, 95%) of the
individual sample results fall below the regulatory decision value. This avoids problems
associated with determining average values. Use of this approach, however, will require a
change in the regulations.
Even when the property of concern is a continuous variable and, therefore, averageable,
collecting representative samples of heterogeneous wastes is often extremely difficult. Many
heterogeneous wastes are discontinuous in terms of physical/chemical properties and, given the
small size of analytical samples relative to the discontinuity, it is not possible to collect (and
demonstrate) representative samples of the wastes. Therefore, to ensure that an adequate
characterization is conducted, a clear definition is needed of what constitutes the "universe or
whole" to be characterized and what constitutes an acceptable level of characterization (i.e.,
What degree of confidence, that the property is below the regulatory threshold, must be obtained
to characterize the waste as nonhazardous.). The universe of the whole must also be defined
to determine the period of time and space in which the samples must be collected.
40
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5.2.2. Regulated Community Perspective
An industrial perspective was prepared by Mr. David Reese, Safety-Kleen Corp., and
presented by Mr. Gene Klesta, Chemical Waste Management Corp. The presentation focused
on the types of samples received at recycle and waste disposal centers and the different types
of problems these materials represent relative to heterogeneous wastes found in the field. The
industry receives large quantities of containerized wastes from different sources which in the
aggregate form a very heterogeneous set.
Industry strongly supports considering the method of management when establishing
analytical requirements. The current requirement for full-scale analysis is, in many cases, not
necessary and represents a significant financial burden for generators and the waste management
industry. The industry recommends that wastes destined for recycling or treatment be exempted
from rigorous analysis if the waste management process and end products are thoroughly
characterized during operations and prior to disposal.
It is further recommended that the Agency permit the use of methods other than those
in SW-846 when conducting acceptance testing of wastes for treatment and recycling. Using
proper QA/QC procedures is adequate to ensure that reliable analysis are conducted. Again,
process monitoring and end product analysis provide sufficient protection of the environment.
The industry will work with the Agency to bring industry-generated methods into the public
sector.
The industry position is similar in concept to the Agency's interest in moving towards
performance-based methods using sound project QA plans, data quality objectives,and accepted
QA/QC procedures as the quality assurance tools to monitor performance.
41
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5.2.3. State-of-Science Perspective
Dr. John Maney, a private consultant, presented a detailed strategy for random and
nonrandom sampling of heterogeneous wastes. The presentation, described a unified way of
looking at all types of waste based on the source and degree of heterogeneity of the material.
Using flow charts and an extensive set of definitions and examples, the paper presents
concrete examples of options available to the field sampling team and the analytical chemist to
generate reliable analytical data from complex, heterogeneous materials. However, unless the
sample undergoes extensive comminution, Dr. Maney indicated that obtaining an analytical size
representative sample of a heterogeneous waste is almost impossible. (See the full paper in
Appendix A for details.).
5.3. CHARGE TO THE WORKSHOP PARTICIPANTS
Before breaking into three workgroups, the participants were asked to address three
questions:
1. Should EPA change from current practice (average testing) to attribute testing for
properties that are not averageable?
2. If so, what is the highest practicable degree of confidence (%) that could be required?
3. Should there be an override that says that if some samples are greater than "X", the
waste is hazardous even if the number of such samples are below the percentage
established in question 2?
A large part of each workgroup's time was devoted to discussion of the practical
definition of attribute testing and how it differs from average property testing. This decreased
42
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the time available to discuss the three issues, so no effort was made to address the third issue
within any workgroup.
5.4. RESULTS OF THE WORK GROUP DELIBERATIONS
5.4.1. Should the Agency Change to Attribute Testing for Properties that are Not
Averageable?
Approximately 90 percent of the participants believed that attribute testing should be
adopted for properties that are not averageable. This approach is more costly than average
property testing in those situations where the average property was determined by compositing
a series of field samples prior to analysis. There was some discussion that compositing of
samples prior to analysis is one way to determine an average property that avoids many of the
technical problems associated with averaging the results from a series of discrete sample
analyses.
Neither the attribute testing nor the average property testing approach eliminates all the
problems associated with the sampling of wastes prior to analysis. The nature of attribute testing
can make the sampling in many situations easier. The group agreed that approximately 80
percent of the error in characterizing waste arises from field sampling error that effects both
approaches equally.
The Agency should focus its efforts on providing sampling guidance for heterogeneous
wastes. Special efforts should be made to provide guidance for specific types of wastes such as
tires, telephone poles, construction debris, and military ordinance. Also, knowledge of the
process that generated the waste is an important part of the decision to use attribute testing and
would be a primary driver in selecting the sampling strategy.
43
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5.4.2. What is the Highest Practicable Degree of Confidence that can be Required?
Several participants felt the answer to this question should take into account the degree
of health and ecological risk associated with the material and the amount (mass or volume).
Therefore, each site should be considered unique and receive individual consideration. A site-
specific degree of confidence should be carefully developed as part of the data quality objective
process and be codified in the site-specific QAPjP.
It was generally agreed that a maximum of 10 percent of samples collected should be
allowed to fail the regulatory criteria. Sixty-six percent of the participants felt that a 4 to 6
percent failure rate was the most appropriate. All participants felt the Agency should publish
clear- guidelines on determining if attribute testing should be applied to a specific situation.
5.5. AGENCY FOLLOW TO WORKSHOP
Subsequent to the workshop, Agency staff met to discuss what steps to take to address
the issue and the ideas presented during the session. It was decided that quantitative data are
needed to determine:
What the practical effect would be if the attribute testing approach was used
instead of the current arithmetic mean.
How the number of samples needed to achieve a defined degree of confidence
would vary across the different types of materials characterized in the RCRA and
CERCLA programs.
During the next year, the Agency plans to examine its data in an attempt to answer the
above questions. However, the Agency will greatly appreciate receiving any additional
information that will help determine if a change in approach will either improve the quality or
lower the cost of decision making. If anyone has data that might assist in this effort, EPA will
appreciate receiving such information. Such information should be sent to the author at the
address indicated in the FORWARD to this report.
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CHARACTERIZING HETEROGENEOUS MATERIALS:
INTRODUCTION
David Friedman
USEPA Office of Research and Development
401 M Street SW
Washington, DC 20460
BACKGROUND
Throughout the RCRA and CERCLA programs, one is faced with the task of
characterizing a material to determine if it possesses some property of concern or interest.
Types of questions one may be answering include:
• Is the material hazardous?
• Can it be safely or successfully managed using a specified treatment technique?
• How much supplemental fuel might I have to add to incinerate the waste?
PROBLEM
When the material being characterized is homogeneous, conventional sampling and
subdividing approaches can be employed. For example, take the case of a truckload of used
foundry sand whose average phenol concentration is of interest. The material is in the form of
relatively fine particles. Conventional compositing and subsampling will provide relatively small
representative samples whose average composition is very close to that of the whole load. The
actual task of obtaining each subsample from the appropriate point in the truck may be very
difficult, but the approach used is relatively straightforward.
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However, what happens when one is faced with a heterogeneous material? When we
speak of heterogeneity, we need to keep in mind that this is a relative term and is a function of
the objectives of the characterization and the analytical sample size. The concern of today's
workshop is generally with wastes of such various particle size, waste consistency or
extraordinary concentration gradients that the sampling and analytical objectives cannot be met
using traditional approaches and standard techniques. When it is not possible to obtain a
representative sample, what shall we do?
This is an important and difficult problem. It is one that has been of concern to many
organizations involved in waste management. For example, in March 1991, the Environmental
Protection Agency, the Department of Energy, and ASTM's Committee D-34 conducted a
workshop to examine how to characterize heterogeneous wastes that were also contaminated with
radioactive materials. A report has recently been issued that describes the results of the
workshop1. However, many problems and issues remain to be addressed and we have
convened today's workshop to address some of the issues.
We would like your help with addressing the following specific issues.
Identify characterization situations that present difficult problems (generically identify
both the type of material and situation).
Develop specific guidance laying out the process to be used to adequately and
cost-effectively address the problem. Describe what criteria should be used to
guide development of solutions/approaches to specific problem situations. Please
be as quantitative as possible on when trade-offs may need to be made and how
to select among options.
If research work needs to be done to develop a solution, please identify what
work needs to be done.
1 Characterizing Heterogeneous Wastes: Methods and Recommendations, EPA/600/R-92/0,
February 1992.
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Since EPA would like to solve monitoring problems through cooperative ventures,
what form should a cooperative development program take? How can it be
organized? Who might the cooperators be?
If you think of any ideas, information, or suggestions that you feel the Agency should
consider when addressing this issue, please send them to us. Send your comments to:
David Friedman (RD-680)
US Environmental Protection Agency
Washington, DC 20460
We will need to receive your comments by August 21,1992 in order for them to be incorporated
into the final conference report.
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CHARACTERIZING HETEROGENEOUS MATERIALS:
REGULATORY PERSPECTIVE
Charles A. Ramsey
USEPA National Enforcement Investigations Center
Box 25227 Building 53 Denver Federal Center
Denver, Colorado 80225
INTRODUCTION
Characterization is the process used to determine whether solid waste is also a hazardous
waste. Characterization is arrived at by following "testing structure." A testing structure is the
particular sampling, analysis, and data interpretation steps that are employed to measure a waste.
The purpose of this paper is to examine the testing structure used to measure characteristics
(ignitability, corrosivity, reactivity, and toxicity) of heterogeneous solid waste that would make
it hazardous waste as defined in 40 CFR part 261.21-24.
To date, there has been little progress in developing a testing structure to characterize
heterogeneous waste. EPA regulations state that characterizing waste includes determining the
average property of the "universe or whole", 40 CFR part 260.10. The problems with the
regulations are that "average" lacks scientific validity and "universe or whole" is not defined.
These two items are an integral part of the testing structure.
To address these problems, two areas must be explored: 1) policy, regulations, and
guidance issues and 2) scientific concerns. This paper focuses on heterogeneous solid waste
because it is a worst case scenario. A testing structure that works for heterogeneous solid waste
will work for any solid waste.
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POLICY, REGULATIONS, AND GUIDANCE ISSUES
Many problems with characterization of heterogeneous materials under RCRA can be
traced to the definition of what type of sample must be collected and analyzed. The required
sample is a "representative" sample which is defined in 40 CFR pan 260.10. "representative
sample means a sample of a universe or whole (e.g., waste pile, lagoon, ground water) which
can be expected to exhibit the average properties of the universe or whole." At least two
problems arise with this definition: what is the average property and what is the universe or
whole?
Average
Does average signify the arithmetic average or the "most likely result" of the target
population? To illustrate, if the data points are 5.7, 5.7, 5.8, 5.9, and 0.2, the arithmetic
average is 4.7. If the regulatory limit is 5.0, the best point estimate of the average is that it is
below the regulatory limit. However, if confidence intervals were required, there would be little
confidence in this conclusion.
If average, however, signifies the "most likely result" (the point at which one half of the
values are above or below-the median) one would conclude that 80% of the data points are
above the regulatory limit. This conclusion is also an expression of a higher degree of
confidence than the conclusion with arithmetic average. More of the values agree with this
conclusion (4 of 5 are above the limit) than agreed with the conclusion based on arithmetic
average (1 of 5 were below the limit).
With the arithmetic average approach, it is possible to have well over half the population
above the regulatory limit and still achieve compliance. With the "most likely result" approach,
not more than one half of the population can be above the regulatory threshold and be in
compliance. The "most likely result" is sometimes referred to as "attribute" testing. An
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attribute testing structure enables one to conclude if a waste is or is not hazardous-not''
degree of hazard.
For clarification of what is meant by average, the Agency provided Chapter Nine of
"Test Methods for the Evaluation of Solid Waste, Physical/Chemical Methods" (SW-846). This
guidance suggests that average signifies the arithmetic average.
A problem with this definition can be illustrated by the following scenarios. One of the
RCRA characteristics is ignitability which includes analyzing samples for flashpoint. The
characteristic is present when the waste flashes at a temperature less that 6CP C. In many cases
a number is not recorded, only the presence of a flash. The regulations do not state that a waste
which flashes at 10° C is any more hazardous than one that flashes at 59° C. This logic fits
well with "most likely result" or percentage (which does not require numeric results), but is
inconsistent with the arithmetic average. With ignitability testing sometimes the analysis
produces numbers and other times it does not. Without numbers, arithmetic averages can not
be calculated, but the "most likely result" can be determined. Another characteristic
corrosivity which can be determined by pH. Several pH values cannot be averaged to determine
the average property of a waste. First of all they are log values and adding them to derive an
arithmetic average is actually a multiplication, thus yielding the wrong information.
Furthermore, from chemical principles, the final pH depends on the buffering capacity of the
individual components. If a waste in question has pH measurements of 2 and 4 (the regulatory
limit under RCRA is 2.S), it is incorrect to conclude that the average pH is 3 and therefore the
waste is not hazardous. Arithmetic average is also not scientifically valid for either toxicity or
reactivity.
Alternatively, the "most likely result" approach will produce valid results for each RCRA
characteristic test. If five samples were randomly selected from a waste and four flashed, then
80% of the samples exceeded the regulatory limit. If "most likely result" is synonymous with
greater than 50%, then the conclusion that the waste is hazardous can be made with confidence.
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Universe or Whole
The waste population to be characterized is not defined in the regulations. If the
"universe or whole" is undefined with respect to both temporal and spatial requirements, it is
not possible to design a valid testing structure. This is illustrated through some of the following
scenarios.
If there are several piles of waste, must a decision be made for each pile or for the whole
of all the piles. What if one pile is above the regulatory limit and the other pile is below? What
if several piles are below the regulatory limit, but a few are above? What if the average is
below; are any of the piles hazardous?
What if the average property of a pile is below the regulatory limit? Some portions of
the pile could be above the limit, and others below. What if the portion of the pile above the
limit was loaded into a truck to be hauled to a non-hazardous waste landfill and this was
sampled? Is this waste which was not hazardous in the pile now hazardous when in the truck?
What if the waste produced today is above the regulatory limit, but the waste produced
yesterday and the waste produced tomorrow is below the regulatory limit, is the waste below
the regulatory limit on average or not?
"Universe or whole" must be defined or it is impossible to know where to sample and
how to interpret the results.
SCIENTIFIC CONCERNS
While it is always possible to sample, analyze and produce data for any waste, the
problem with heterogeneous materials is the confidence that a correct compliance decision was
made based upon a valid testing structure. A compliance decision is affected by the purpose of
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the measurement, use of proper sampling and analytical methods, and correct interpretation of
the results. The variability within heterogeneous materials exacerbates the bias and imprecise
of the results. As bias and imprecision increase and the average approaches the regulatory limit,
compliance decisions become more difficult. If, however, the proper testing structure was
employed, it would dramatically improve the decision making process and increase the
confidence in the results.
A proper testing structure should have the following characteristics:
It must be scientifically valid. Basic scientific principles must not be violated. There
are instances where the ideal scientific solution can be adjusted for simplicity, politics,
and economics, but the solution must remain scientifically valid. Agency regulations,
policy, and guidance must never be inconsistent with basic scientific principles
("Safeguarding the Future: Credible Science, Credible Decisions", EPA/600/9-91/050).
It must be consistent. All elements of the testing structure are dependent on each other
for their validity. Sample collection must anticipate the analyses and data interpretation
to be performed to ensure that the proper samples are collected. Likewise, without
detailed knowledge regarding sample collection, data interpretation is meaningless.
Proper Sampling
Proper sampling primarily depends on the regulatory question (e.g., presence, trends,
absence, etc.), the universe or whole (population), and the confidence that the correct
compliance decision can be made. These three considerations-question, population,
confidence-must be definitively addressed before a sampling plan is developed and implemented.
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Proper Analysis
Proper analysis for RCRA characteristics is not an issue, because three of the four
characteristics have required test methods referenced in the regulations (reactivity methods are
only guidance at this time). The correct analytical result is the one obtained by following the
prescribed analytical method.
Proper Data Interpretations
Proper data interpretation is important for making correct decisions. Data interpretation
ties the analytical results back to the population with some specified degree of confidence to
determine if the sampling and analysis answered the question about the waste. Proper data
interpretation includes:
Making the proper type of confidence statement. The statement does not need to be
statistical; it can be an expression of professional judgment If statistical statements are
made one must recognize that there are many types (e.g., confidence interval of the
mean, tolerance limits, prediction intervals, etc.). Not all statistical statements are valid
for any particular compliance problem and care must be chosen to select the correct one.
Establishing degree of confidence in the statistical statement. It is possible that one can
make a certain statistical statement (or use professional judgment), but if one is not very
confident in the statement it serves no purpose proving compliance or non-compliance.
With many types of statistical statements, certain assumptions are made regarding the
distribution of the data. If incorrect assumptions are made, the resulting statistical statement and
degree of confidence might not be correct. The guidance given in SW-846 makes certain
assumptions regarding the distribution of data (normally distributed) which are usually incorrect.
By definition, heterogeneous waste (as well as most environmental data) defies these assumptions
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to a degree that can make the decision and confidence statements based on arithmetic aver
incorrect. The usual indicators of non-normal data are outliers and skewed distributions. Wt.
the "most likely result" no distribution is assumed (non-parametric) and therefore the problems
with heterogeneous waste do not affect the accuracy and confidence of the decision.
CONCLUSIONS
Characterization of heterogeneous waste depends on the development on a valid testing
structure. Currently, only portions of the testing structure are in place. Two items that need
to be addressed are:
The "most likely results" (percentage) is the valid statistic for making compliance
decisions to characterize waste. The current use of arithmetic average is scientifically
invalid for the RCRA characteristics and can lead to wrong compliance decisions. There
are at least two percentage options that currently exist in the RCRA regulations. One is
the empty drum regulation (40 CFR part 261.7) which states that drums with a capa
of less than or equal to 110 gallons are considered empty if no more than 3 % is left (arid
the contents have been removed using common practices). Drums with a capacity of
greater than 110 gallons are allowed 0.3%. The other percentage option is found in the
Land Ban regulations (49 CFR part 268) which requires that no more than 1% of the
population can be over the treatment standard.
With this new system, the Agency must decide what percentage of the waste it
will allow to be over the regulatory limit and still classify the waste as non-hazardous.
To be the most protective of the environment, 0% should be adopted although it is
probably an unrealistic standard.
"Universe of whole" must be clearly defined. This is not a scientific issue, but rather
a policy issue, The term requires clarity and specificity as to both time and space. Some
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examples might be: one day of production, one week of production, one pile, all piles
currently on the property, 100,000 Kg, etc. Defining "universe or whole* as one waste
stream would ignore the temporal problems. Without knowledge of exactly what the
waste population is in terms of both time and space, it impossible to develop a testing
structure to characterize it
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WASTE CHARACTERIZATION:
INDUSTRY PERSPECTIVE
David Reese
Safety-Kleen Inc.
PO Box 92050
Grove, IL 60009-2050
INTRODUCTION
Heterogeneous as defined by Webster in the context of a waste is "consisting of dissimilar
or diverse ingredients or constituents". The complexity of this issue is illustrated with a drum
of heterogeneous waste in figure 1.
Characterization of heterogeneous wastes presents a number of unique challenges for'
industrial community. The principal challenges are: sampling, methodology of analysis,
frequency of testing, and controlling/ reducing costs.
SAMPLING TECHNIQUES
Routine sampling techniques consisting of sample segregation, compositing,and particle
size reduction are often inappropriate when trying to homogenize a heterogeneous waste.
Collecting the sample can become a formidable task when the waste is comprised of multiple
large particle size components. SW-846 sampling containers often are not suitable for sample
containment and larger vessels are required. Loss of volatiles due to headspace in the vessels
affects the validity of the results. Present particle size reduction techniques such as grinding
only exacerbates the problem by driving off volatiles.
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TESTING REQUIREMENTS AND PROCEDURES
State and Federal regulations often require extensive testing protocols in Waste Analysis
Plans (WAPs) and permits. Regulators routinely require the use of SW-846 analytical methods.
These methods often are not appropriate for a variety of waste streams (organic solvents, oily
wastes, by products of recycling such as distillation bottoms). The use of methods other than
SW-846 should be accepted for alternative test procedure approval and not rejected on the sole
basis they are not SW-846. Most of the quality assurance/ quality control principals and
guidelines can be incorporated into alternative test methods resulting in improved data with only
procedural and or hardware modifications. Unfortunately these methods are not considered valid
by regulators.
The present sampling and testing requirements fail to consider the volume and frequency
of the waste being handled. It is extremely costly to test every fifty-five gallon drum according
to SW-846 guidelines, while testing every incoming rail car might be feasible. Current sampling
frequencies often overlook one of the key issues facing a heterogeneous hazardous waste
handler, that being, the end use of the waste. If small volumes of wastes are going to be mixed
with other wastes for processing in terms of recycling, and the facility is permitted to handle the
waste, the result will have no impact on the process, thus, sampling and testing need to reflect
the use of the waste while providing a safe working environment. The product of the process
should become the focus of testing.
Continuing the status quo will drive many companies out of business and create large
companies which will monopolize hazardous waste handling while passing the costs on to the
generator and ultimately the consumer. This is due to the excessive costs associated with testing
every handled waste. Multiple testing of the same waste is redundant and provides no greater
assurance of safety, process control, product quality.
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CONCLUSIONS: DEVELOPING ALTERNATIVES
Recognize Alternative Test Methods
State and federal regulators must become accepting of industry generated methods of
analysis for complex waste streams handled on a daily basis.
Develop New Methods
EPA in conjunction with industry should work together to facilitate the rapid development
and approval of new methods. This could be accelerated by ming industry developed methods.
Encourage Recycling
Recycling needs to be encouraged by minimizing input testing and focussing *—
by-products of the process. When a facility is fully permitted to handle wastes, analysis dt
not affect the processing or end use. This adds unnecessary costs to the recycling process
through testing of incoming, in process, and final products.
Account for End Use
Prescribing testing must account for the end use of the waste. Some end uses such as
alternative cement kiln fuel present minimal hazards, thus testing should be relevant to the waste
destination.
Balance Cost with Severity of Hazard
The health and safety models need to be incorporated into the testing protocol by
focussing on hazards and not over testing of materials mat pose little or no threat.
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Obstacle to Implementation
The largest obstacle for implementation of the above alternatives is the magnitude of the number
of individual state regulators with differing view points. The result of negotiating fifty different
WAPs in fifty states poses limitations on industries ability to comply fully at all times. It is
impossible for a business to operate fifty different ways on the same type of waste stream.
REFERENCE
Characterizing of Heterogeneous Wastes: Methods and Recommendations; EPA 600/R-92/033,
Feb. 1992
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CHARACTERIZING HETEROGENEOUS MATERIALS:
SCIENTIFIC PERSPECTIVE
John P. Maney, Ph.D
Environmental Measurements Assessments
5 Whipple Road
Hamilton, MA 01982
INTRODUCTION
A discussion of heterogeneous waste characterization is best started with a brief review
of definitions. .
Sample: a part or piece taken or shown as representative of a whole group. (Webst
Unabridged Dictionary, Second Edition)
Sampling: the act, process or technique of selecting a suitable sample..;/ .
(Webster's 7th Collegiate Dictionary)
Representative Sample: A sample of a universe or whole (e.g. waste pile, lagoon,
ground water) which can be expected to exhibit the average properties of the universe
or whole. (CFR 260.10)
Homogeneous: uniform structure or composition throughout.
(Webster's 7th Collegiate Dictionary)
After studying the above definitions and applying them to waste characterization, it
becomes apparent that sampling of an ideal homogeneous waste will always result in a sample
that represents the properties of the waste (assuming that the sampling process itself does not
introduce contamination or allows for selective loss of waste components).
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Heterogeneous: consisting of dissimilar ingredients or constituents. (Webster's 7th
Collegiate Dictionary)
Unfortunately, many of the real-world wastes are not homogeneous, but are
heterogeneous, which makes collection of a representative sample a challenging tasy. Prior to
discussing the representativeness of heterogeneous wastes, the following points can be made
regarding homogeneity and heterogeneity.
• Homogeneity and heterogeneity are diametric terms.
• Homogeneity and heterogeneity are relative to objectives.
• Homogeneity and heterogeneity are related to spacial and temporal distribution.
• Homogeneity and heterogeneity are sample size dependent.
A determination regarding the homogeneity and heterogeneity of a waste is made by
comparing the visual, physical or chemical composition or properties of different samples. The
more heterogeneous a waste is, the less homogeneous it is and vise-versa. Thus, when either the
homogeneity or heterogeneity of a waste is defined the other is also defined. This relationship
should be kept in mind, since for the sake of readability, the remainder of this discussion will
often refer to only one term.
Heterogeneity is relative to objectives and perspective. A non-random mixture of fine
silver nitrate powder and large crystals of silver nitrate will be considered to be heterogeneous
by the analyst performing particle size determination while the analyst performing the TCLP for
lead would consider the material homogeneous. Likewise, while the chemical properties of
99.99999% pure uranium are homogeneous, a nuclear chemist may consider it highly
heterogeneous on an isotopic level.
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The spatial or temporal distribution of dissimilar waste constituents or concentre'"—*s
gradients can also affect the measured heterogeneity of a waste. If a representative distril
is spread over a greater area or length of time than that represented in a sample, then sample
to sample heterogeneity will be greater than when a sample encompasses the distribution of the
dissimilar waste components or concentration levels. For example, the measured heterogeneity
of an effluent, whose concentration of phenol linearly cycles from lOOppm to 5ppm and back
to lOOppm every two minutes, will be a function of what portions, or if the entire cycle is
included in sequential samples.
Assuming that the concentration of the target parameter varies with particle size, sample
to sample heterogeneity will depend on whether a sample is not only large enough to
accommodate all the different sized constituents of a material but will also depend on whether
the sample is large enough to accommodate representative amounts of the various sized
constituents of a waste. To better understand this concept consider a 2 liter waste container that
has one gram nuggets of cadmium randomly distributed through-out an otherwise homogeneous
and cadmium free matrix. If one gram samples are collected and analyzed for cadmium,
sample to sample heterogeneity of the waste will vary dramatically and will depend upon
whether the sample did or did not contain a cadmium nugget. However, the heterogeneity will
appear to be substantially less if 30 gram samples are collected and analyzed in total for
cadmium. Thus the measured heterogeneity of the same waste varies according to the size of the
sample. That is why for the following discussion, unless otherwise indicated, the sample size
used to determine heterogeneity of a waste will be the analytical sample size. Heterogeneity of
a waste will be measured according to the ability of an unaltered analytical sample to
reproducibly represent the average properties and/or chemical constituents of the waste unit of
interest. (The analytical sample is the mass/volume of sample submitted to analysis not the field
sample, e.g. the 1 to 2 gram sample required by the acid digestion specified in Method 3050 .
Unaltered means that the sample was not subjected to homogenization or pulverization steps. A
waste unit is the population or unit of waste that is being subjected to evaluation, e.g. drum, a
wastepile or landfill).
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Representative Database: a database, generated by the collection and analysis of more
than one sample, which together represent the average properties of the universe or
whole.
It is often impossible to collect a single sample which is representative of a heterogeneous
waste. The average properties of a heterogeneous waste are better represented by collecting a
number of waste samples such, that all portions of the waste under study have an equal chance
of being sampled. Analyses of these samples can be compiled into a database which should be
representative of the waste. It is more correct to think of a representative sample in terms of a
representative database, which is closer to the statistical use of the term, sample.
In light of all the attention directed towards heterogeneous waste, it is important to note
that from a sampling perspective, the significance of heterogeneity is not in this quality, itself,
but in the fact, that heterogeneity hinders or prevents the generation of a representative database.
The need for representativeness is the driver behind the interest and studies into heterogeneous
waste characterization.
Random: being a member of, consisting of, or relating to a set of elements that have
a definite probability of occurring with a specific frequency; being or related to a set
whose members have an equal probability of occurring. (Webster's 7th Collegiate
Dictionary)
Randomness is a critical factor in the characterization of hazardous waste. Accurate
characterization requires that the sampling process reflect the randomness or lack of randomness
of the waste. If the waste parameter of interest is distributed in a random fashion a proper
randomly designed sampling program should generate a representative set of samples. If the
waste parameter is not randomly distributed (refer to discussion of strata in the following
section) then a simple random sampling plan may not accurately characterize the waste.
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TYPES OF HETEROGENEOUS WASTE
If the average properties of the waste unit of interest is not reproducibly represented in
analytical samples, then the material is considered heterogeneous. Such heterogeneous wastes
can exist in many forms;
RANDOM HETEROGENEOUS
• Randomly heterogeneous in composition/property.
• Randomly heterogeneous in particle size.
• Randomly heterogeneous in particle size and composition/property.
NON-RANDOM HETEROGENEOUS (STRATIFIED)
• Non-randomly heterogeneous in composition/property.
• Non-randomly heterogeneous in particle size.
• Non-randomly heterogeneous in particle size and composition/property.
EXCESSIVELY NON-RANDOMHETEROGENEOUS (EXCESSIVELYSTRATIFIED)
• Excessively non-randomly heterogeneous in composition/property.
• Excessively non-randomly heterogeneous in particle size.
• Excessively non-randomly heterogeneous in particle size and
composition/property.
Assuming that all particle sizes in the waste can be accommodated by the analytical
sample size and that the analytical method is applicable to all waste constituents, then randomly
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and non-iandomly heterogeneous waste can be characterized by a database generated from the
collection and analysis of random or systematic samples. Regarding non-randomly heterogeneous
waste a more precise estimate of mean (representative) concentrations can be obtained with a
stratified sampling approach.
Excessively non-random heterogeneous wastes are defined as those wastes that have
such dissimilar components, that it is not practical to use traditional sampling approaches to
generate a representative database. Nor would the mean concentrations reflected in such a
database be a useful predictor of a given subset of the waste that may be subjected to
evaluation, handling, storage, treatment or disposal, (i.e. the level of uncertainty is too
great).
Stratum: a portion or subgroup having a consistent distribution of the target
parameter, and a different distribution than the rest of the waste.
Waste strata can be thought of as different portions of a waste population, which may
be separated in time or space or by waste component, and each portion has internally similar
concentration distributions of the target parameter, through-out A landfill may display
spatially separated strata, since old cells may contain different wastes than new cells. A
wastepipe may discharge temporally separated strata, if night shift production varies from the
day shift.
There are wastes which do not display any identifiable temporal or spacial
stratification, yet the target compound distribution is excessively erratic. For these wastes it
may be helpful to consider a third type of stratification - stratification of the waste by waste
component.
Component: A waste component is any identifiable article, discrete unit or
constituent of the waste, which is randomly or non-randomly distributed through-out
the waste.
Prvtaaed at EfA WoHatap m July 16.1992
gateaa Materials' C~21
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Stratification by waste component is easily applied to wastes that contain easily
identifiable particles such as large crystals or agglomerates, rods, blocks, gloves, pieces of
wood, concrete, etcetera. Strata separated by waste component is a different but key concept.
Separating a waste into strata according to waste components is useful when a specific kind
of waste component is not randomly distributed through-out the waste and when a
contaminant or property of interest is correlated with the waste component. This type of
strata is different since the components are not necessarily separated in time or space but are
usually intermixed and the properties or composition of the individual components are the
basis of stratification. For example, automobile batteries which are mixed in an unrelated
waste would be a waste component which could constitute an individual strata if lead was a
target parameter. If one were to sequester the batteries they would have a consistent
distribution which was different from the rest of the waste. However, if the concentration of
the target parameter is similar in different components and the particle size is such that all
the components are represented in the chosen sample size, then there is no purpose in
stratifying by waste component. Strata, by component is an important mechanism for
understanding the properties of excessively non-random heterogeneous waste and for
designing appropriate sampling and analytical efforts for these types of waste.
Table 1 summarizes mechanisms for segregating strata as well as the discriminating
qualities of strata. Since the mechanism and qualities are independent of each other there are
a total of 9 possible types of stratified wastes.
PraaaedatEPA WorUiapIBJmfy 16.1992
•Omeuripng Haovgeuaa Uaterteis ' C-22
-------
TABLE 1. Strata Considerations
Mechanism for Segregating Strata
Spacial
Temporal
Component
Discriminating Qualities
Composition/Property
Particle Size
Composition/Property and Particle Size
The contamination in different strata are often generated by different processes. The
different geneses of the contamination will usually result in a different concentration distribution
and mean concentrations. Thus, each strata will have their own distribution and mean
concentration levels. If a waste having strata of distinctly different concentration distributions
is sampled using a simple random sampling approach, the concentration distributions of the
different strata may result in a bi-modal or multi-modal distribution. Homogeneous and randomly
heterogeneous waste, which are not stratified will display a normal unimodal distribution. See
Figure 1.
Non-randomly heterogeneous waste will usually have a limited number of strata which
can be identified and sampled individually or sampled as one waste. When different strata are
sampled as one population, the properties of the different strata are averaged. If the different
strata are similar in composition, then the average concentrations will be a good predictor of
composition for subsets of the waste and will often allow the program objectives to be achieved.
As the difference in composition between different strata increase, the average values become
less useful in predicting composition/properties of individual portions of the waste, which may
be handled separately. In this later case, it is advantageous to sample the individual strata
separately and if an overall average of waste composition is needed, it is best calculated
mathematically using statistical information from each strata.
Excessively non-random heterogeneous waste has numerous strata, each of which contain
different distributions of contaminants and/or particle sizes, such that an average value for the
Presented at EPA Weriahcp WJufy 16. 1992
'Oaraaerizasg Heerogmeaa Mataieb' C-23
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Normal Bell Distribution
(Gaussian)
Concentration
Bimqdal
Distribution
Concentration
Concentration
Figure 1: Types of Concentration Distributions
Pnsaiud at EPA Workshop IHJmfy 16,1992
•Omoeriatg JUumgouau Hounds'
C-24
-------
waste would not be useful in predicting the composition or properties of individual portions of
the waste (i.e. statistically speaking the variance and standard error of the mean will be large).
The line of demarcation between non-random heterogeneous and excessively non-random
heterogeneous waste is not hard and fast. A waste can be considered excessively non-random
heterogeneous when mean values will not be representative of most portions of the waste and
when it is so heterogeneous that the waste cannot be cost-effectively sampled using traditional
sampling approaches and meet the project objectives.
A theoretical example of an excessively stratified waste could consists of commingled
waste from:
Source A - which generated a waste of varying particle size with a mean antimony
concentration of 20ppb and a standard deviation of 7ppb.
Source B - which generated a waste of varying particle size with a mean antimony
concentration of TOOOppm and a standard deviation of SOOOppm.
Source C - which generated a waste of varying particle size with a mean antimony
concentration of 3% and a standard deviation of 2%.
Source D - which generated a waste of varying particle size with a mean concentration
of 81% and a standard deviation of 17%.
To further complicate the above waste, imagine the waste being commingled with other
materials of various particle size that may or may not contain various contaminants in addition
to antimony.
To improve readability, the remainder of the document will refer to non-random
heterogeneous waste as stratified waste and excessively non-random heterogeneous waste as
excessively stratified waste.
Praaaat el EPA Workshop Witty 16. 1992
'Oaraatriang Hoerogoteau Mauriais ' C~25
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^ the same tetter htenns of ihe
are waste constituents which are" kJaifcSloJbawr
Homogeneous
'AAAABA/T
/ABAAABABAABt"
BAABAAAABBAA'
/ABA8ABABABABAB1
/BABABABABABABAB)
ABABABABABABABAJ
\BABASABABABABAI
VBB8BBBBBBBBBB,
1BBBBBBBBBBI
Stratified
Excessively Stratified
or
Random Heterogeneous
rjxip
:xx*x*xx:
:xxx;
:xxxx«
;xxx:
< X X X X XN
YYYYYY
'YYYY
/YYYYY
'YYYYY^I'YYYYYYl
'YYYYYj ^YYYYYY/
rz*.zi
Stratified
As can be seen in the stratified
heterogeneous waste above.
heterogeneity can vary over
time.
Figure 2: Types of Positional Distributions for
a Waste Unit Such as a Landfill
PnsaaaiaEPA Wartahop m JOy 16,1992
'Ounaovmg Uaengateaa ttataielf
C-26
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This figure depicts the process
by which a waste is classified
as a particular waste type.
This classification wifl be
based upon knowledge of the
waste, observations, or ideally
- preliminary sampling of the
waste.
If no significant variation is
detected between random
samples, the waste can be
considered homogeneous.
The waste is a heterogeneous
waste B there is variation
between individual samples.
if the waste constituents are
randomly districted
through-out the waste, the
waste would be a randmory
heterogenous waste, if
information describes a
correlation between waste
variation and time or spatial
variations or with certain waste
components or particle size.
then the waste would be
classified as a stratified or
excessively stratified waste.
Wastes that can be
cost-effearvety sampled to
meet-project objectives would
be classified as stratified
wastes. Those wastes which
consist of such strata that they
cannot be cost effectively
sampled are classified as
excessively stratified waste.
Knowledge
Observations
Preliminary Sampling
Homogeneous
Waste
N
I
[Variation between
Samples
1
Randomly
Heterogenous
Variation Correlates with
Time, Space, Particle
Size, or Components
Can Waste Be Cost-effectively
Sampled to Meet Objectives
N
Excessively Stratified
Waste
Figure 3: Process for Classifying Wastes
Praaaai at EPA Wortthap UJJuly 16.1992
'OtaraaeriaHg Haerogaieaa Materials'
C-27
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Table 2 details some of the issues and concentration distributions that are pertinent to the
different types of heterogeneous wastes. For example, sample size, the number of sampl
sample locations are not an issue when sampling a homogeneous waste, while they are critical
issues when attempting to collect a representative sample of a heterogeneous waste.
PARTICLE SIZE AND SAMPLING THEORY
As a result of a continuing need to improve environmental data, it has been recognized
that sampling is presently the greatest contributor to imprecision and inaccuracy. To minimize
this error, many have correctly turned to the mining industry, which has a relative wealth of
sampling theory and expertise. The theory and applicable expertise of the mining industry has
recently been documented by a recognized expert on sampling, Francis F. Pitard, (Pitard,
Francis F., "Pierre M. Gy's Sampling Theory and Sampling Practice, CRC Publishers). This
theory, which not only applies to field sampling but also to subsampling performed in the
laboratory - determines sample mass/volume as a function of the maximum particle size of the
material being sampled..
Based on the maximum particle size of a material, sampling theory suggests minimum
sample sizes (refer to Table 3.) and particle size reduction of the sample to minimize sampling
error. For example, a waste having a maximum particle size of 0.5 inches would require
collection and analysis of a minimum sample size of 2 Kilograms to keep the sampling error less
than 17%. Since a 2 kilogram sample is too large to be subjected to analysis, it would have to
be subjected to particle size reduction prior to analysis.
It would be very costly to routinely use existing sampling theory to minimize sampling
error. These increased costs would be driven by the large sample sizes and the requirement to
reduce particle size.
The large sample sizes, specified to minimize sampling error, would increase costs since;
Prague* at EPA Weriahep DlJufy If. 1992
•Omaamg Hatngouxmi Materials' C-28
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• Sample containers and coolers would be larger and more numerous
• Larger samples would be shipped
• Larger sample storage and sample handling areas would be needed
• Large volume of unused samples would increase disposal costs.
• Health and Safety costs associated with exposure to larger samples.
Particle Size Reduction, (PSR), also has a substantial impact on cost because of the
manpower and capital investment for the required crushing and pulverizing equipment. In
addition the following are reasons for concern if particle size reduction was to be implemented
on a large scale;
• Laboratory contamination from fines.
• Damage to instrumentation from fines.
• Difficulty in cleaning PSR equipment to prevent cross-contamination.
• Loss of volatile and labile compounds and elements.
• Generation of a sample which has different properties and thus yields different
analytical results than the original sample.
• Increased Health and Safety Costs
Fortunately, the costs of employing large sample sizes and particle size reduction can
often be minimized if the waste history and Data Quality Objectives are communicated to and
discussed with the lab staff and field personnel.
Presented at EPA Wortshap W July 16,1992
'Otaraaeriang Haeroftaeaa Haerials' C'29
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TABLE 3. SUGGESTED SAMPLE SIZE BASED ON MAXIMUM PARTICLE SIZE
ACCORDING TO PIERRE GY'S SAMPLING THEORY
SUBSAMPLE SIZE MAXIMUM PARTICLE SIZE
(grams) (centimeters)
1 .1
2 .13
3 .14
4 - .16
5 .17
10 .21
20 .27
30 .31
40 .34
50 .37
75 .42
100 .46*
"The Toxicity Extraction Procedure and the Toxicity Characteristic Leaching Procedure allow
samples to contain particles as large as .95 centimeters.
Waters and soils can be contaminated in numerous ways, the most common mechanisms
being; direct discharge of the contaminant onto the soil or water and atmospheric fall-out from
fires, fugitive emissions, vents and stacks. Soils can also become contaminated from adsorption
of groundwater or surface water contaminants while waters can become contaminated by mixing
with contaminated waters or by leaching contaminants from contaminated soils or wastes.
Wastes can be contaminated by many mechanisms during generation or by mixing with
other wastes or further contaminated by the mechanisms described in the previous paragraph.
The different types of contaminants are aqueous liquids, non-aqueous liquids, gases, small to
large particles and multi-phased mixtures.
Praaaed at EPA VartOtef BZJtfy 16.1992
•Oienaaitatg Oeengaamt Hounds' C-30
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How a contaminant will be dispersed in the matrix will be determined by the mechanism
of contamination, the type of contamination, the surface area and adsorptive properties of the
sample matrix, gravity, physical manipulation and the physical size of the contaminant at the
time of contamination. (Eventually, fate and transport will substantially affect dispersion of
contaminants.) The physical size of the contaminant can be referred to as the contaminant unit
and can be measured in centimeters. Liquids, dissolved contaminants and gases have a
contaminant unit on a molecular or atomic level, (e.g. atoms can be on the order of 1 X 10-8
centimeters in diameter). Solids and suspended solids contaminate on a microscopic to
macroscopic level, (i.e. their Contaminant Unit is equal to their particle size).
Particle size can have an impact on sampling error even when the contaminant unit is on
the atomic scale, if matrix particles are of different sizes and have different adsorptive
properties. If adsorptive properties are similar for different size particles, then the dramatically
larger surface area of smaller particles/volume would result in more atomic scale contaminants
being adsorbed to smaller particles. (Thus one could eschew particle size reduction, (PSR), and
still employ a smaller subsample size by excluding large particles, if the ease of using a smaller
sample size out-weighed the chance of a false-high concentration.)
When the contaminant unit is on a larger, particle scale then adsorptive properties of the
matrix will not affect contaminant distribution in the sample. For microscopic and macroscopic
particles, an accurate representation in the subsample will be affected by the number of particles
and the relative size of the particles to the subsample size. Microscopic particles will have a
contaminant unit substantially smaller than the sub-sample size and these small particles should
not be discriminated against during subsampling.
When the contaminant unit is macroscopic and approaches the size of the sample, the
error in sampling will increase, if large sample sizes or PSR is not employed. If the largest
particle size in the sample correlates with the contaminant unit, then the large sample size
specified by sampling theory pertains to the waste. As the contaminant unit becomes smaller as
Pnsaaat a EPA Wortshap m J*fy 16. 1992
'Oaraaeriting Haerogeneoui ifaeriaJj ' C~31
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compared to the size of the sample, the greater the opportunity to avoid PSR and to select -jv
exclude larger particles from the sample without introducing substantial error., (If desii
weight of the excluded particles can be used in the calculation of a final concentration. However,
this could result in a false low result, since the contamination, if any, associated with the large
particles is not accounted for.)
The mechanism of contamination, the type of contaminant and the contaminant unit will
impact the complexity and potential error of sampling. These impacts may be better understood
by reading the following examples.
Example 1
TYPE OF CONTAMINANT: Particles contaminated with lead
MECHANISM: Direct discharge of particle to soil
CONTAMINANT UNIT: Particles as large as 0.3 centimeters
AVERAGE LEAD CONCENTRATION: lOppm
HISTORY: A manufacturer of lead-alloy babbitt lining for bearings, stored its machining
waste in piles behind it facility. Periodically the machining wastes would be recycled into
new babbitt linings. After SO years of employing this practice, the soil became
contaminated with particles of babbitt having a maximum particle size of 0.3 centimeters.
The contaminated soil consisted mainly of fine silts with less than 10% consisting of
gravel with stones having diameters ranging from 2 to 3 inches. The sampling team
uncovered a problem when they referred to the specified "minimum sample size" for 3
inch particles (i.e. 450kg). The problem of large sample size was avoided, since the
sampling team was aware of the "Type of Contaminant" and the "Mechanism" of
contamination and the "Contaminant Unit". Knowing that lead contaminated particles
were discharged directly to the soil, the sampling team was able to discard the large
stones with the realization that by discarding the stones, the resulting lead concentrations
would be a worst case. (The small lead contaminated particles would preferentially exist
in the fine silts as opposed to being adsorbed to the large stones and if lead had
dissolved, the dissolved lead would tend to adsorb to the silt which has the much larger
surface area.) The sampling team collected approximately 250 mis of soil and delivered
them to the laboratory for analysis.
Praaaed at EPA Wortahap OfJtfy 16,1992
•Oumaaiang Hoavgateno iiouriols- C-32
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The analyst referred to sampling theory (refer to Table 3.) and determined that the
minimum sample size for a sample with a maximum particle size of 0.3 centimeters was 30g.
(The small percentage of larger gravel was not used to determine the maximum particle size.)
The analyst split the sample into 30g aliquots and randomly chose one for analysis. Since
the analyst did not have particle size reduction equipment and the largest sample volume he
could analyze was approximately 10 grams, he split the chosen aliquot in thirds and analyzed
all three for lead. After analysis, the concentrations were averaged.
Example 2
TYPE OF CONTAMINANT: Ionic lead dissolved in an aqueous solution (Atomic scale)
MECHANISM: Direct discharge to soil
CONTAMINANT UNIT: Atomic scale, (approximately 1 X 10-8 centimeters for atoms
and somewhat larger for ion diameters)
AVERAGE CONCENTRATION: 10 ppm
HISTORY: The above described babbitt manufacturer also employed an acid-treatment
process. The aqueous waste was discharged into a tank which allowed the lead
contaminated water to leach into the surrounding soils. The surrounding soils consisted
of fine silt with 15% of its volume consisting of stones ranging in size from 0.25 to .5
inches. The sampling team collected a 2 Kilogram sample to minimize the sampling
error. The samples were sent to the laboratory for analysis. Since the analyst knew that
the soil was contaminated by lead on an atomic scale, he discarded the small stones, split
the sample and analyzed a 2 gram aliquot. (The analyst knew that the much higher
surface area of the silt would have adsorbed orders of magnitude more lead than the
stones, so that this approach yielded a worst-case analysis. To check this hypothesis, the
analyst performed an acid leach on a few stones and no detectable quantities of lead were
measured.)
The above examples show how, with knowledge of the type and mechanism of
contamination and the contaminant unit the sampling team and the analyst can decrease the costs
of handling large samples and particle size reduction without substantially increasing sampling
Praaued at EPA Workshop m July 16.1992
'OiaraaenaHf Haerogoteats Materials' C~33
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error. Without the site history, large sample sizes or particle size reduction would havr
required or one would risk the introduction of a substantial error into the measurement process.
Thus communication with the analyst regarding the type and mechanism of contamination is an
important means of controlling costs and minimizing errors.
The above sampling strategies are not ideal since they allow for assumptions and
interpretation and these assumptions and interpretations could lead to substantial intentional and
unintentional errors. However, the above sampling strategies are more practical, more likely to
be implemented and may be a significant improvement over the alternatives. Lastly, when these
sampling strategies are implemented by an experienced personnel who are aware of the DQOs,
site history, the types and mechanisms of contamination and the contaminant unit, the errors
associated with interpretation and assumptions should decrease substantially.
It is important to note, that application of these sampling strategies to wastes is much
more difficult than for soils and subsampling of wastes may frequently require a f ' *
application of sampling theory. Wastes are a more difficult media, since the complexity
waste generation often preclude knowledge of how a contaminant of interest is dispersed within
a waste and whether distribution will be a function of particle size.
EXCESSIVELY STRATIFIED WASTES
The remainder of this discussion will concentrate on excessively stratified wastes, the
most difficult wastes to characterize. Compositional or particle size heterogeneity or a
combination of both compositional and particle size heterogeneity can be the cause of excessive
stratification. This discussion will address each of these causes and will concentrate on sampling
issues, since sampling is now recognized as the greatest contributor to imprecision and bias.
However, before addressing the different causes of heterogeneity, it will be useful to
consider an issue which should be common to all waste characterization efforts.
fraaaed at EPA Wortxtop mitfy 16,1992
•CharaaeriziHg Haengattsm* Materials • C-34
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The first step in characterizing any heterogeneous waste is to gather all available information on
the;
• Need for waste characterization,
• Objectives of waste characterization,
• Pertinent regulations, consent orders, and liabilities,
• Sampling, shipping and laboratory health and safety issues,
• Generation, handling, treatment and storage of the waste,
• Existing analytical data and exacting details on how it was generated,
• Treatment and disposal alternatives.
These types of information will be used in the planning of the sampling and analytical
effort. The planning process should be detailed and address the issues defined in EPA's data
quality objective (DQO) process. The different disciplines ( e.g. sampling, chemistry,
engineering, statistics needed to properly understand and exploit the above types of information
must be present during the planning process. If enough information is available, the planning
process will uncover the existence of excessive stratification which will prevent achievement of
objectives. If information is lacking, a preliminary sampling effort would be advisable, and if
done properly should detect the existence of excessively stratified wastes.
Excessively stratified waste can not be cost-effectively characterized by traditional
methods and this fact usually becomes apparent during the planning process. The following
discussion will consider approaches which in effect will lessen the level of stratification and
allow for more cost-effective characterization. Some of these approaches will require changes
in objectives, waste handling or disposal methods, and some will require compromises, but all
approaches will require the above types of information.
Proaaed at EPA Wortshcp IB July 16. 1992
'Oiamaeriang Haerogauats Materials' C~35
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Of the following types of excessively stratified waste, the difficulty in characterr
waste increases from those that have strata based solely on particle size, to those which ca._
of compositional strata to those which have strata of varying composition and particle size. In
fact, the difficulty in characterizing waste, which consists of strata of different particle size, is
simply a matter of determining that composition is constant across different particle sizes. If the
composition is found to be constant across the different particle sizes, the waste should be easily
characterized.
The more problematic types of waste, which have enumerable strata of different
composition or a combination of different composition and particle size are much more difficult
to characterize. The approach to characterizing these wastes usually has to be determined on an
individual and unique basis.
Excessive Strata of Different Sized Particles
Wastes having excessive stratification due only to different sized particles wil
definition have the same composition or property (i.e. homogeneous or randomly heterogeneous)
through-out its different strata. The strata can be separated in space or in time. Unless one is
attempting to measure particle size, this waste is the simplest of the excessively stratified waste
types to characterize. All particles in these types of wastes are usually generated by the same
process, (e.g. smelter slag and the previous example of silver nitrate powder and crystals),
which is the reason for similar composition across all particle sizes.
The complexity of dealing with these types of wastes is in proving that the waste has
similar composition, (i.e. mean levels and concentration distribution of the parameter of interest)
across the varying particle sizes. This determination can be made by using knowledge of the
waste or by sampling the different sized particles to determine if there are significant
compositional differences. If the determination is made using knowledge of the waste, it is
advisable to at least perform limited sampling to confirm the determination.
Praauat at EPA Wortsltep BZJtfy 16.1992
'Ouroaaiang Haerogauaa Hatoialt' C*36
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The characterization process is greatly simplified, once a determination has been made
that the waste has similar composition or properties across the various particle sizes. The
sampling and subsequent analysis can be performed on particles which are readily amenable to
the sampling and analytical process and the resulting data can be used to characterize the waste,
in its entirety.
It is important to periodically verify the assumption that the different particle sizes are
composed of materials having the same concentration levels and distributions of the contaminant
of interest. This verification is especially important when there are any changes to the waste
generation, storage, treatment or disposal processes. Similarity of composition between particles
has to be verified for each parameter of interest. The effect of different particle size must also
be considered when measuring properties such as the Toxicity Characteristic Leaching Procedure
(TCLP) .
Excessive Strata of Different Composition or Composition and Particle Size
Wastes having excessive stratification due only to composition or property will have
similar particle size through-out its different strata. The strata may be separable in space, time
or by component or source. Stratifying the waste should simplify the characterization process.
Wastes having excessive stratification due to both composition/property and particle size
are usually the most difficult wastes to characterize. The strata can be separated in space, in
time, or by component or source.
Figure 4. summarizes an approach to characterizing these types of excessively stratified
wastes. If a waste is excessively stratified, traditional methods of sampling will not allow
objectives to be cost-effectively achieved. To cost-effectively sample an excessively stratified
waste, one must use a non-traditional approach. The non-traditional approach may involve
modification to the sampling, sample preparation or analytical phase of the process. If after
frooaed at EPA. Workshop OH July 16. 1992
'Characterizing Haerogoieeus Materials' C~37
-------
Figure 4. Approach for the Characterization of Heterogeneous Waste
Is Waste
Excessively Stratified?
J
Can Sampling Be Modified?
"I-
Can Sample Prep
Be Modified?
Change Handling,
Treatment,
Disposal of Waste Or
Target Parameter
Change Sampling
and
Analysis
Objectives
N
N
N
N
Use Traditional Random.
Stratified or Systematic
Sampling
Will Modified
Approach
Allow Waste
to Be
Cost-Effectively
Sampled
And
Objectives
To Be Met?
Figure 4: Approach for the Characterization of Heterogeneous Waste
fraaued at EPA Werfcfop OUsfy 16.1992
•Ooaeuritmt Haerggauaa UaaUs"
C-38
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modifying the approach to sampling and analysis the objectives still can not be achieved in a
cost-effective manner, then the original plan of waste handling, treatment or disposal has to be
examined and changed so the waste can be characterized according to new and achievable
objectives.
The following subsections discuss approaches that can be employed to make excessively
stratified waste more amenable to a cost-effective sampling approach.
Design of the Sampling Approach
The first efforts to resolve the difficulty in characterizing an excessively stratified waste
are usually focused on the sampling aspects of the project. This is a logical place to start and,
if a successful sampling approach is designed, the project objectives can be cost effectively
achieved.
The difficulty in sampling excessively stratified waste can result from:
1) Various particle sizes and waste consistency which makes sampling difficult and
traditional sampling approaches cost prohibitive.
2) Extraordinary concentration gradients between different components or
enumerable strata that lead to such excessive variance in the data, that project
objectives can not be achieved.
3) Wastes which exhibit both of the above properties.
A strategy for designing a sampling plan for such excessively stratified waste includes
the following five steps;
Presented a EPA Wortshep m July 16. 1992
•Oanaersaif Haerogtneaa Materials' C-39
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1) Select the target parameters.
2) Determine whether these parameters are correlated with; particle size space time
components, or sources.
3) Determine if any waste components or strata can be eliminated from sampling
because they do not contribute significantly to the concentration of the target
parameter.
4) Determine if small particles in a stratum represent the stratum as well as large
more difficult to sample particles. If yes, sample the smaller particles and only
track the volume contribution of the larger particles. (See Particle Size and
Sampling Theory).
5) Determine if contamination is innate or surface adsorbed. Is the contamination
surface adsorbed which would allow the material to be representatively san.
by wipe sampling? Can large particles be wiped and smaller particles extracted,
leached or digested. Can waste be stratified according to impervious and non-
impervious waste and sampled and analyzed accordingly?
To understand how this strategy would work, consider a hypothetical scenario - a storage
area containing 4000 drums of waste generated over a 15 year period. The drum contents are
excessively stratified and contain a myriad of wastes from process waste; destruction and
construction debris such as wood, concrete; lab wastes including broken glassware, paper, empty
bottles; etcetera. The appearance of the combined drum contents could best be described as a
municipal landfill in drums which appears impossible to characterize.
Praaaed a EPA Workshop m Jafy 26.1992
mgauna Haloids ' C-40
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1) WHAT ARE THE TARGET PARAMETERS?
None of the waste contents are known to be listed waste so the target parameters are the
TCLP and other hazardous waste characteristics. In addition, groundwater modeling has
indicated that the storage area is the source of a plume contaminated with solvents and
beryllium.
2) ARE THE TARGET PARAMETERS CORRELATED WITH AN IDENTIFIABLE
STRATA OR SOURCE?
The source of beryllium is traceable to one process, whose waste should be easily
identifiable if drum markings are not legible enough to determine the source. The solvents are
likewise traceable to a machine shop which would have disposed of its waste in easily identified
drums.
Testing will have to be performed to determine if there is any correlation with particle
size, space, time or components in the waste.
3) CAN ANY WASTE COMPONENTS OR STRATA BE ELIMINATED?
Historical information indicated that 400 drums of construction debris were generated
during construction of a new warehouse. The information indicates that the virgin nature of the
materials may make these drums candidates for not sampling or less intensive sampling.
Likewise, the source of beryllium contamination is a beryllium sludge which exists in
drums by itself or in drums commingled with shredded packing material and laboratory wastes
that were generated during physical testing of the beryllium product. If the materials commingled
with the beryllium waste are known not to be a source of contamination, the commingled
framed at EPA Workshop HJufylf. 1992
•OnmaeTtaig Haerogaieaa Mauriali• C-41
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material can be discriminated against during sampling and only the beryllium sludge sampled
and the volume contribution of the commingled material noted.
4) ARE CONTAMINATION LEVELS CORRELATED WITH PARTICLE SIZE?
Some of the older beryllium sludge has dried and formed a cementaceous aggregate of
different particle sizes. Since the sludge is known to be homogeneous within a batch by process
knowledge and preliminary sampling data, sampling can be restricted to the more easily sampled
- smaller particles sizes.
5) IS CONTAMINATION INNATE OR SURFACE ADSORBED
The waste from the machine shop consists of varied material from fine metallic filings
to large chunks of metal and out-of-specification metal product. Since the only contamir '-n
in the machine shop is solvents and cutting oils and the waste matrix is imperviou.
contamination is surface adsorbed in nature. Thus sampling of these wastes will consists of the
sampling of fines which will be subjected to extraction, wipe sampling of the large metallic
objects and notation of the volume contributions of the different particle sizes.
It is essential that all assumptions , (i.e. any correlations), be verified by at least
knowledge of the waste and preferably confirmed by exploratory sampling and analyses.
In the above hypothetical case, the proposed strategy for characterizing the 4000 drums
resulted in:
The identification of two large strata that constitute the majority of the waste (i.e. the
beryllium sludge and the solvent and cutting oil contaminated machine shop waste).
The elimination of the need to sample 10% of the drums, (i.e. the construction debris),
if preliminary testing verifies waste disposal information.
PnsauatalEPA Wohahep m Jufy 16.1992
•Otaraaaaan Haengeuaa Materials' C-42
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Simplified sampling of the beryllium commingled waste by restricting sampling to the
beryllium sludge and not the other commingled materials.
Simplified sampling of the cementaceous beryllium sludge by limiting sampling to the
more easily sampled small particles.
Simplifying the sampling of the machine wastes since the source of contamination is
surface adsorbed and not innate to the waste materials.
A less expensive and doable sampling design which will result in a more precise estimate
of the mean and will generate strata specific information which will be valuable if the
strata are eventually treated separately.
The following subsections describe additional strategies that can be employed if the above
sampling strategies are not applicable to a waste or if they are applicable but by themselves will
not allow the project objectives to be cost-effectively met.
Modification of the Sample Preparation Method
As discussed in the Introduction, heterogeneity is analytical sample size dependent. The
greater the particle size and the greater the variance of the concentration of the target parameter,
the greater the heterogeneity for a given analytical sample size. To minimize the measured
heterogeneity and to accommodate large particle sizes, traditional sample preparatory methods
can be altered.
In the laboratory, the term "sample preparation" is commonly meant to include two
separate steps; 1) the subsampling of a field sample to generate an analytical sample, and 2) the
preparation of the analytical sample for subsequent analysis.
Regarding subsampling, the previously discussed logic for field sampling (refer to Section
3.1.1) is also applicable for the generation of analytical samples. That is, knowledge of
concentration distributions within the waste can be used to simplify subsampling by:
Praautd at EPA Workshop IB July 16.1992
'Oumoeriang Jieurogmeaa Materials' C-43
-------
1) Eliminating any waste components or strata that do not contribute signifies to
the concentration of the target compound;
2) Discriminating against large particles and only select small particles if small
particles represent the waste as well as large particles; and.
3) Surface wiping larger particles and extracting or digesting fines if surface
contamination is the source of the target parameter.
If the above approaches are not applicable to a field sample, the field sample will have
to be subjected to particle size reduction (PSR) prior to subsampling or the sample preparation
method will have to be modified to accommodate the entire field sample.
PSR is useful for handling field samples, which have particles too large for proper
representation in an analytical subsample. The intent of PSR is to decrease the maximum particle
size of the field sample so that the field sample can then be split and or subsampled to ge
a representative subsample. The difficulties in applying PSR to waste samples are:
1) Not all materials are easily amenable to PSR (e.g. stainless steel artifacts);
2) Adequate PSR capabilities and capacities do not normally exist in environmental
laboratories;
3) PSR can change the properties of material ( e.g. leachability)
4) PSR can be a source of cross-contamination; and
5) PSR is often not applicable to volatile and labile compounds.
fntaaedaEPA VaHattof UUtfy 16. 1992
amgouout Materials' C-44
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Modification of sample preparative methods can include the extraction, digestion or
leaching of much larger sample masses than specified. The advantage of this approach is that
the resulting extract, digestate or leachate are relatively homogeneous which simplifies
subsampling. This approach is particularly important for volatile organic compounds which may
suffer from substantial losses if subjected to PSR. For volatile organic compound analysis, larger
portions of the wastes can be subjected to methanol extraction or possibly the entire field sample
could be subjected to heated headspace analysis as one sample or as a series of large aliquots.
Prior to modifying a sample preparatory method, especially a method associated with a
property such as the Toxicity Characteristic Leaching Procedure (TCLP), it is advisable to
consult the end-user of the data and the pertinent regulator if appropriate.
Modification of Analytical Method
The analytical phase of a sampling and analytical program allows another opportunity to
simplify the characterization of an excessively heterogeneous waste. Examples of different
classes of analytical methods are ;
Screening methods,
Portable methods,
Field Laboratories methods,
Non-intrusive methods,
Innovative methods, and
Fixed laboratory methods.
Screening, portable and field laboratory methods have the distinct advantage that they
allow for the cost-effective analysis of more samples. These methods not only generate more
precise data but the greater number of samples make it easier to detect correlations between
concentration levels and waste strata or components. Also some screening methods may analyze
a larger sample volume than what is traditionally submitted to a fixed laboratory.
Praaaal at EPA Woriahap BJJ*fyl6.1992
'Otaraaeraaig Haavgoicaa Maurialt' C-45
-------
Non-intrusive methods can be useful when there are health and safety issues regarding
exposure to the waste. These methods may also be used to qualitatively or semi-quanti' sly
evaluate large volume wastes.
An EPA Document entitled "Characterizing Heterogeneous Wastes EPA 600/R-92/033"
has a solid discussion of non-intrusive methods and new methodologies that are being developed
for the characterization of heterogeneous wastes.
Modification of the Waste Handling, Treatment Disposal Plan
If the modifications discussed in the previous subsections are not applicable to a given
waste or when they are applicable but still do not allow the objectives to be cost-effectively met,
then the reasoning behind the original program must be examined. The original need behind the
waste characterization objectives has to be examined and an approach for simplifying the
characterization process must be devised.
For example, assume that the need behind waste characterization objectives for a c
program was the common requirement to determine if a waste is hazardous prior to waste
disposal. An initial attempt to characterize the waste; 1) failed to meet the objective, 2) indicated
that the waste was excessively stratified, and 3) proved that portions of the waste are hazardous.
After reviewing this preliminary information and the costs to attempt a defensible
characterization of the waste, it could be decided that all the waste will be assumed to be
hazardous and treated as hazardous waste. Under this scenario, the needs change and now
compliance with the land-ban requirements may become the issue. Assume that the waste was
incinerated, then the less heterogeneous and more easily sampled incinerator ash would be
sampled in lieu of the original excessively stratified waste.
An other example would be a large laboratory operation that generates drums of gas-
chromatography (GC) vials containing dissolved standards, solvents and numerous contaminants
Praaaed a EPA Wartsliep mJufy 16.1992
'Oanaermg Haerogautms Materials' C-46
-------
extracted from samples of different origins. Although, the vial contents were individually
analyzed by GC for certain parameters, the contents were not analyzed for enough parameters
to characterize the waste. A quick review of this waste would preclude further and cost
prohibitive analyses of every vial. Thus, an alternative approach would have to be devised. An
alternative approach could require that the vials be crushed and the vial contents and the solvent
used to rinse the broken vials would be collected in a receiving drum. This approach would
convert drums which contained hundreds of different vials, each of which could have their own
independent concentrations of contaminants, into two relatively homogeneous waste strata, i.e.
solvent rinsed glass and contaminated solvent.
CONCLUSIONS
The previous discussion reviewed heterogeneity issues and proposed a single and
systematic approach to the characterization of hazardous waste. This approach is based upon the
evaluation of wastes in terms of their degree and type of stratification • a factor which drives
the degree of difficulty in sampling a particular waste.
This discussion also proposed stratification in an additional dimension than the traditional
spatial and temporal dimensions. The stratification of waste according to waste components and
sources can simplify the characterization process and provide needed strata information.
This systematic approach and the additional mechanisms for stratifying waste is intended
to aid in the characterization of wastes especially those that are excessively stratified.
Presented a EPA Wahahap Jtt July 16.1992
'Oanaermg Heterogeneous Materials ' C-47
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•o
•o
CD
D
0.
x"
X
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Appendix XIII
Improper Hazardous Waste Characterizations:
Financial and Compliance Implications
-------
,»/«
i»
WILLIAM F. COSULICH ASSOCIATES, P.C.
ENVIRONMENTAL ENGINEERS, SCIENTISTS AND PLANNERS
QUALITY ASSURANCE IN
ENVIRONMENTAL MONITORING
IMPROPER HAZARDOUS WASTE CHARACTERIZATIONS
FINANCIAL AND COMPLIANCE IMPLICATIONS
By
RICHARD M. WALKA
WILLIAM F. COSULICH ASSOCIATES, P.C.
WOODBURY, NY
(516) 364-9880
FRANK A. LANGONE
INTERNATIONAL BUSINESS
MACHINES CORPORATION
RICHARD P. RUSSELL
WILLIAM F. COSUUCH ASSOCIATES, P.C.
EBC013
-------
IMPROPER HAZARDOUS WASTE
CHARACTERIZATIONS—FINANCIAL AND
COMPLIANCE IMPLICATIONS
Richard M. Walka
Richard P. Russell
Frank A. Langone
This paper is not a "how to" on when or under what circumstances one is required to
make a hazardous waste determination, or a primer reviewing a step by step approach to
rendering a proper characterization. Rather, the purpose of this paper is to illustrate why
generators of waste should render accurate and well-founded determinations as to whether the
material is a hazardous waste pursuant to appropriate federal and/or state requirements. The
paper will also review the potential financial and compliance implications of managing
nonhazardous waste as hazardous waste in New York State. When waste is classified as
hazardous, its management requires the use of a manifest for off-site transportation. Utilizing a
manifest results in a number of explicit and implicit protections and liabilities. The implications
of using the hazardous waste manifest will be a major portion of the discussion.
The recognition of the uniform hazardous waste manifest among waste generators across
the nation is probably second only to the IRS 1040 Form. Since its creation by the
Environmental Protection Agency in the late 1970's, the hazardous waste manifest and the vast
information network it supports, remains the cornerstone of RCRA's national "cradle to grave"
hazardous waste tracking system. We will explain why the manifest possibly has more
responsibilities than protections associated with its use.
It has been our experience that some clients firmly believe that "when in doubt" waste
should be classified as hazardous. These clients assume mat transporting the material as a
hazardous waste, with an accompanying manifest, is always "safer", affording mem some
protection mat ordinarily would not otherwise exist. This "protective filer" mentality has a
number of enforceable regulatory liabilities, as well as financial implications, associated with it
which can be burdensome when the facility actually does not generate any hazardous waste.
These considerations are in addition to the high cost of hazardous waste disposal.
Obviously, this paper supports utilizing the hazardous waste manifest when appropriate,
and fosters the concept of proper and judicious hazardous waste characterizations. However, we
are opposed to using hazardous waste manifests when solely generating/transporting,
nonhazardous industrial waste.
Before we discuss the financial and compliance liabilities associated with transporting
manifested nonhazardous waste, we will briefly describe the hazardous waste program.
OIORMWJUT
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WHEN IS A WASTE A HAZARDOUS WASTE?
Section 1004(5) of RCRA defines hazardous waste as a "...solid waste, or combination
of solid wastes, which because of its quantity, concentration or physical, chemical or infectious
characteristics may:
(A) cause or significantly contribute to an increase in mortality or an increase in serious
irreversible, or incapacitating reversible illness;
or
(B) pose a substantial present or potential hazard to human health or the environment
when improperly treated, stored, transported or disposed of, or otherwise managed."
While this statutory definition is subjective, it clearly states that in order for a material
to be a hazardous waste, it must first be a "solid waste", as defined by RCRA. In order for a
solid waste to be defined as a hazardous waste, it must meet the following conditions:
Is not excluded from regulation as a hazardous waste, and;
• Exhibit any of the characteristics of a hazardous waste, and/or;
• Be named a hazardous waste and listed by regulation as such, or;
Is a mixture containing a characteristic waste/listed hazardous waste and a
nonhazardous solid waste, unless the mixture is specifically excluded or no longer
exhibits any of the characteristics of hazardous waste. A mixture containing a
nonhazardous waste and a listed hazardous waste will remain a listed hazardous
waste.
In the preceding section, we provided a general definition of hazardous waste. However,
there are two principle mechanisms to determine whether a waste is a hazardous waste. First,
one must determine if it is a "listed waste," so named because it is specifically listed as such by
the EPA or a State as part of its hazardous waste regulations. Secondly, based on knowledge or
laboratory analysis, one must determine if it exhibits any characteristics of a hazardous waste:
ignitability, corrosivity, reactivity and toxicity.
CHARACTERISTIC WASTE
Ignitability
A solid waste that exhibits any of me following properties is considered a hazardous waste
due to its ignitability:
A liquid, except aqueous solutions containing less then 24 percent alcohol, that has
a flash point less than 60°C(140°F);
010RMWJUT
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• A nonliqirid capable under normal conditions of spontaneous and sustained
combustion;
• An ignitable compressed gas in accordance with Department of Transportation
(DOT) regulation;
• An oxidizer per DOT regulation.
EPA's reason for initially including ignitability as a characteristic was to identify waste
that could cause fires during transport, storage or disposal.
Corrosivitv
A solid waste that exhibits any of the following properties is considered a hazardous waste
due to its corrosivity:
An aqueous material with pH less than or equal to 2.0 or greater than or equal to
12.5;
A liquid that corrodes steel at a rate greater than 0.25 inch per year at a temperature
of 55°C (130°F).
EPA chose pH as an indicator of corrosivity because waste with high or low pH can react
dangerously with other waste or cause toxic contaminants to migrate from certain waste. Steel
corrosion was chosen because waste capable of corroding steel can escape from its container.
Reactivity
A solid waste that exhibits any of the following properties is considered a hazardous waste
due to its reactivity:
• Normally unstable and reacts violently without detonating;
• Reacts violently with water;
• Forms an explosive mixture with water;
Generates toxic gases, vapors or fumes when mixed with water;
• Contains cyanide or sulfide and generates toxic gases, vapors or fumes at a pH of
between 2 and 12.5;
OIORMW.RPT
-------
• Capable of detonation if heated under confinement or subjected to strong initiating
source;
• Capable of detonation under standard, temperature and pressure;
• Listed by DOT as Class A or B explosive.
Reactivity was chosen as a characteristic to identify unstable waste that can pose a
problem at any stage of mat waste management cycle.
Toricitv
The toxicity characteristic test is designed to identify waste likely to leach particular toxic
constituents into the groundwater as a result of improper management.
To ascertain if a solid waste is hazardous because of the toxicity characteristic,
constituents are extracted from the waste hi a manner designed to simulate the leaching action
which occurs in landfills. The extract is then analyzed to determine if it possesses any hazardous
constituents listed in Table 1. If the concentrations of the toxic constituents are equal to or
exceed the regulatory levels listed, the waste is classified as hazardous.
Characteristic hazardous wastes are defined by certain physical/chemical criteria which
may require a representative waste sample analysis by the generator. The Toxicity subcategory
is more likely than the other characteristics to require chemical analysis. Consequently, a waste
generator must be very careful in selecting/paying for the correct protocols to characterize his
waste for Toxicity.
There are financial implications tied to Toxicity wastes in two areas. First, the prescribed
leaching protocol (Toxicity Characteristic Leaching Procedure - TCLP) is an expensive protocol
to run. However, it may not be required if the waste is a 100% solid matrix or a solid/water
matrix, for which a total constituent analysis has been performed. The extraction is also not
required if the waste is a liquid with no solid phase. Thus, an understanding of when the TCLP
is needed has a significant influence on the cost of waste characterization.
Secondly, it is important to compare the appropriate Toxicity analytical result with the
regulatory level to avoid incorrect hazardous waste determinations (false positives) which will
result in the compliance/financial implications that will be discussed below. For example, the
total constituent analysis of a 100% solid waste sample would be reduced by a factor of 20,
before comparing it to the regulatory level (the 1 to 20 factor is derived from the 1 to 20 dilution
factor mat is part of the TCLP protocol).
A good source of information on the entire Toxicity category and, in particular, on
correctly using the TCLP procedure/interpreting analytical results is: "Technical Assistance
Document for Complying with the TC Rule and Implementing the Toxicity Characteristic
Leaching Procedure (TCLP)", May 1993, U.S. EPA-Region H.
010RMW.RPT
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Table 1
TOXICITY CHARACTERISTIC CONTAMINANTS
AND REGULATORY LEVELS
Carbon totnchlondc
o-Cnool
m-Cresol
p-Cresol
Cresol
2.4-D
1.4-Dichteobenzene
EPA Hu&rdoos
Waste Number Contemtoflnfa
D004
DOOS
D018
D006
D019
D020
D021
D022
D007
D023
D024
D02S
D026
D016
D027
D028
D029
D030
D012
D031
DQ32
O033
O034
DOOS
D013
D009
D014
D035
O036
D037
DOSS
D010
DOIl
D039
D01S
D040
D041
D042
D017
D043
1.1-DicUotoettaylan
2.4-Doimtalaeoe
Eadrm
Hexaditoioiij-butBdieBe
Lead
Ladane
Moony
Methyl ethyl ketono
Fyridmo
Setanmn
SOver
ToncUoreetiiyieBe
Tnduoroctnyteno
2,4,6-TridiIoropteiol
Z.4&IP (S3v«)
Vinyl diteride
Oironlc Toxidty Ref-
erenee Level fmg/D
0.05
. 1.0
0.005
0.01
0.005
0.0003
1
0.06
O.OS
2
2
2
2
0.1
0.075
0.005
0.007
0.0005
0.0002
0.00008
0.0002
0.005
0.03
0.05
0.004
0.002
0.1
2
0.02
1
. 0.04
0.01
0.05
0.007
0.005
0.005
4
0.02
0.01
0.002
MCL
MCL
MCL
MCL
MCL
RSD
Rfl)
USD
MCL
RfD
RfD
RfD
Rfl)
MCL
MCL
MCL
MCL
RSD
MCL
RSD
ESD
MCL
MCL
MCL
MCL
KID
BID
RfD
Rfl)
MCL
MCL
pgp
MCL
MCL
RfD
pgn
MCL
MCL
Pxn-m Rjsk-Spflcific DOM '' '
RfD • Referenco Dose
* The regutooiy terel cquab'tho ebranie toxicity reference level ti»n a dilurion/attei
Levd frng/D"
5.0
100.0
OJ
1.0
OJ
0.03
100.0
6.0
5.0
200.0*
200.0'
200.0*
200.0*
10.0
715
0.5
0.7
0.13'
0.02
0.008
0.13'
OJ
3.0
5.0
0.4
0.2
10.0
200.0
2.0
100.0
5.0*
1.0
5.0
0.7
OJ
0.5
400.0
2.0
1.0
r (DAK) of 100, imlias etfaenrin noted
' If o-. m-. and p-creaol conctnarationi cannot be differentiflled, the total cnaol (D026) coneenmtion a uaed. Note that D026 was added to the final rale for this
purpoe, but is not« new eonainttait
* The quantitanon limit (Le, five tmei the detection limit) is greater than the calculated regulatory level; thus, the qu
nes the regulatory level
Source: 55 S11804 and 11815-11816.
. 1-24-94
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LISTED WASTE (SPECIFIC/NONSPECIFIC)
As we mentioned above, solid waste is considered hazardous waste if it is "listed" as one
of the following:
• Nonspecific source waste - These are generic wastes, commonly produced by
manufacturing and industrial processes. Examples from this list include spent
halogenated solvents used in degreasing and wastewater treatment sludge from
electroplating processes.
Specific source waste - This list consists of wastes from specifically identified
industries such as wood preserving, petroleum refining and organic chemical
manufacturing. These wastes typically include sludges, still bottoms, wastewaters,
spent catalysts and residues; e.g., wastewater treatment sludge from the production
of pigments.
• Commercial chemical products - The third list consists of specific unused
commercial chemical products or manufacturing chemical intermediates. The key
criterion for this category is that the waste is unused, e.g., off-spec or spilled
materials. This list includes chemicals such as chloroform and creosote, acids such
as sulfuric acid and hydrochloric acid, and pesticides, such as DDT and kepone.
These lists were developed by examining different types of waste and chemical products
to ascertain if they:
• Exhibit one of the four characteristics of a hazardous waste(listed above);
• Meet the statutory definition of hazardous waste;
• Are acutely toxic or acutely hazardous;
• Are otherwise toxic.
It should be noted that individual States may designate additional materials as listed
hazardous wastes. For example, New York State regulates PCB wastes as listed hazardous
wastes (B-codes).
010RMW.RPT
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REGULATORY REQUIREMENTS
If a facility produces hazardous waste based on the regulatory criteria discussed above,
it may be classified as a hazardous waste generator. Hazardous waste generators are the first link
in the "cradle to grave" hazardous waste management system established pursuant to the Resource
Conservation and Recovery Act (RCRA). Generators of 100 kilograms of hazardous waste or
1 kilogram of acute hazardous waste per month must comply with certain enforceable generator
standards.
The pretransport regulatory requirements for hazardous waste generators include:
• Obtaining an EPA ID number. One way that EPA monitors and tracks generators
is assigning each generator a unique identification number. Without this number,
the generator is barred from treating, storing, disposing, transporting or offering for
transport any hazardous waste to any transporter or treatment, storage or disposal
facility;
• Adhering to procedures for handling hazardous waste before transport;
• Manifesting hazardous waste for off-site transportation;
• Maintaining a 24-hour Emergency Contact for each shipment;
• Record keeping and reporting;
• Proper packaging to prevent leakage of hazardous waste during normal transport
conditions and in potentially dangerous situations (e.g., when a drum falls out of a
truck);
• Identifying the characteristics and dangers associated with the waste being
transported through labeling, marking and placarding of the packaged waste;
• Preparing applicable Land Disposal Restriction (Land Ban) shipping notices.
It is important to note that these pretransport regulations only apply to generators shipping
waste off-site.
In addition to the requirements outlined above, EPA and authorized states also developed
pretransport regulations for accumulation of waste prior to transport. A generator can accumulate
hazardous waste on-site for 90 days or less without a permit, as long as the following
requirements are met:
• Proper Storage - The waste is properly stored in containers or tanks marked with the
words "Hazardous Wastes" and me date on which accumulation began. The waste
must also be inspected at least weekly and inspections records maintained
010RMW.RPT
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• Emergency Plan - A contingency plan and emergency procedures to use in an
emergency must be developed.
• Personnel Training - Facility personnel must be trained in the proper handling of
hazardous waste.
• Preparedness and Prevention Measures - Providing adequate security measures,
signage, and communication systems.
The 90-day period allows a generator to collect enough waste to make transportation more
cost-effective; that is, instead of paying to haul several small shipments of waste, the generator
can accumulate waste until there is enough for one large shipment.
THE HAZARDOUS WASTE MANIFEST
The manifest is the fundamental element of the hazardous waste tracking system. The
uniform hazardous waste manifest is the document which accompanies shipments of waste and
tracks the material from the generator (the cradle) to the ultimate disposal facility (the grave).
The RCRA manifest requires the following information:
Name and EPA identification number of the generator, transporter(s) and the facility
where the waste is to be treated, stored or disposed;
U.S. DOT description of the waste being transported;
Quantities of waste being transported; and
Address of the treatment, storage or disposal facility to which the generator is
sending the waste.
• 24-hour emergency contact telephone number.
It is especially important for the generator to prepare the manifest properly, since the
generator is responsible for the hazardous waste produced and its ultimate disposition.
Waste Minimization
When Congress passed the Hazardous and Solid Waste Amendments (HSWA) in 1984,
it established a framework aimed at eliminating specific forms of waste management such as land
disposal, in favor of more technologically advanced, permanent destruction methods, such as
incineration.
Among its complex and far reaching provisions, the HSWA contained a statutory
provision which initiated waste minimization criteria. Sections 3002(a)(6), regarding the
preparation of biennial waste reduction reports, and 3002(b) of HSWA, entitled, "Waste
Minimization", require generators of hazardous waste to practice and report on waste
minimization activities. It requires generators of hazardous waste to sign a specific certification
010RMW.RPT
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on the manifest indicating that they are doing all that is "economically practicable" towards
reducing the volume or quantity and toxicity of the hazardous waste generated at a facility. It
is a signed certification that generators are in full compliance with HSWA waste minimization
criteria.
Section 3002(b) of HSWA, entitled "Waste Minimization", reads as follows:
"(b) Waste Minimization - Effective September 1, 1985, the manifest required by
subsection (a)(S) shall contain a certification by the generator that -
(1) the generator of the hazardous waste has a program in place to reduce the
volume or quantity and toxicity of such waste to the degree determined by the
generator to be economically practicable; and
(2) the proposed method of treatment, storage, or disposal is mat practicable
method currently available to the generator which minimizes the present and
future threat to human health and the environment."
With regard to the requirement for biennial reporting of waste reduction efforts to
regulatory agencies, Section 30021(a)(6) reads as follows:
"(6) submission of reports to the Administrator (or the State agency in any case in
which such agency carries out a permit program pursuant to this subtitle) at least
once every two years, setting out -
(A) the quantities and nature of hazardous waste identified or listed under this
subtitle that he has generated during the year;
(B) the disposition of all hazardous waste reported under subparagraph
(C) the efforts undertaken during the year to reduce the volume and toxicity
of waste generated; and
(D) the changes in volume and toxicity of waste actually achieved during the
year in question in comparison with previous years, to the extent such
information is available for years prior to enactment of the Hazardous and
Solid Waste Amendments of 1984."
In addition to these enforceable waste reduction mandates brought about by the HSWA
manifest certification, many states have already passed additional statutes and regulations to
address pollution prevention and waste reduction.
For example, in August 1990, New York State passed a law requiring facilities that
generate and have the potential to release hazardous wastes and toxic substances into the
environment reduce, to the maximum extent possible the volume or quantity and toxicity of
wastes, whether emitted into the air, discharged into the waters, or treated and disposed of in a
010RMW.RPT
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permitted facility. The waste reduction may be achieved by implementing technically feasible
and economically practicable waste reduction technology, process or operation changes. The
legislature declared that implementing such measure will help the State achieve an overall
reduction in the generation and release of hazardous waste of fifty percent over the next ten (10)
years.
This law requires generators of hazardous wastes to prepare, implement and submit a
Hazardous Waste Reduction Plan (HWRP) to the New York State Department of Environmental
Conservation (NYSDEC). The HWRP, which is reviewed for acceptance by NYSDEC, must be
updated biennially and annual status reports must be submitted. Failure to submit an acceptable
plan precludes the generator from signing the hazardous waste manifest certification.
The requirements of the Hazardous Waste Reduction Plan include, but are not limited to,
the following:
• Quantification of hazardous waste(s)
• Description of hazardous waste source(s) of generation and disposal method(s)
• Indices of hazardous waste generation to production (i.e. output from, or input to,
the process generating the waste stream)
• Submission of a hazardous waste generator summary
• Cost estimates) for managing each waste
• Evaluation of technical feasibility and economical practicability of implementing
waste reduction options
• Listing of technically feasible and economically practicable waste reduction
measures and schedule for implementing identified waste reduction measures
Description of corporation's and facility's waste reduction policy
Identification of party responsible for implementation of waste reduction plan
Identification of waste reduction measurement(s)
• Identification of employee training programs
• Estimate of anticipated hazardous waste reduction
Estimate of anticipated transference of hazardous waste into other environmental
media
Submission of Hazardous Waste Reduction Program Summary (HWRP)
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Biennial updates of HWRP
• Annual Status repOItS
In addition, to the state statute, EPA has published its interim final rule regarding waste
minimization program requirements. Although published in the Federal Register as an interim
final rule, the guidance puts "additional enforcement teeth" behind the hazardous waste manifest
certification requirements mandated by the Hazardous and Solid Waste Amendments.
TAX ASSESSMENT/REGULATORY FEES
In addition to the regulatory/compliance implications discussed above, there is an
additional liability when hazardous waste is generated at your facility and properly managed via
a manifest, or a nonhazardous waste is accompanied by a manifest. That liability is a special
assessment and regulatory fee. In New York State, these assessments and fees are administered
by the New York State Departments of Taxation and Finance and Environmental Conservation,
respectively. The "bottom line" is that the generation of hazardous waste in New York State can
affect your "bottom line." Another good reason to make sure your hazardous waste is in fact,
hazardous. Let's briefly review the two revenue programs.
As mentioned above, the first tax, entitled, "Special Assessments on Generation, Treatment
or Disposal of Hazardous Waste in New York State" is administered by the Department of
Taxation and Finance and is self reported by generators and TSDFs within the state on Form TP-
550. This self reporting program is managed comparable to other state taxes, that is, it is
prepared and reported by the generator and subject to review and audit by the Department of
Taxation and Finance. In its simplest form, the Special Assessment, or "waste end assessment"
as it is commonly referred to, is calculated by generators based on the tons of hazardous waste
generated in New York State mat received on site treatment or disposal or that were designated
for removal or removed from the site of generation for treatment or disposal or for storage prior
to such treatment or disposal during the reporting period. With regard to treatment and/or
disposal facilities, these entities are only required to report the tons of hazardous waste received
from generators outside New York State for treatment disposal or for storage prior to such
treatment or disposal (this avoids double counting.)
In accordance with the Environmental Conservation Law (§27-0923 Special Assessments
on Hazardous Wastes Generated) the following assessment rate schedule currently applies:
Assessment Rate
Category (in dollars per Ton)
Tons disposed of in landfill on-site of generation $27
Tons designated for removal or removed from the site of
generation for disposal in a landfill or designated for
removal or removed from the site prior to disposal in a landfill .... $27
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Tons designated for removal or removed from the site of generation
for treatment or disposal (except by landfill or incineration), or for
storage prior to such treatment or disposal $16
Tons designated for removal or removed from the site of
generation for incineration or for storage prior to incineration $ 9
Tons incinerated on the site of generation $ 2
'Tons received from out-of-state for landfill
disposal or for storage prior to such disposal $27
Tons received from out-of-state for treatment or disposal other man
landfill or incineration, or for storage prior to such treatment
or disposal $16
Tons received from out-of-state for incineration or
for storage prior to incineration $ 9
As can be seen from the table above, the rates are structured to provide an incentive for
disposal/treatment of waste by incineration and discourages disposal via landfilling. A deduction
may be taken for waste mat is reclaimed
These special assessments are paid quarterly and are due to the Department by the 20th
day of the month after the end of each calendar quarter. While the fees may not seem onerous
at first glance, it does not take much material to achieve a ton of waste. For instance, a 55
gallon drum of water (the density used to calculate the fee) weighs approximately 459 Ibs or
approximately .23 of a ton. So one can see how quickly the special assessments can take a bite
of your bottom line.
The second financial implication of generating hazardous waste is the Regulatory Fee,
which is administered by the New York State Department of Environmental Conservation
pursuant to 6 New York Codes, Rules and Regulations Parts 480 through 486 (Revised 1991).
Unlike the "waste end assessment" discussed above, the Hazardous Waste Program Fee
prescribed in Part 483 is an invoice prepared and sent by the Department based on data from
annual generator reports and manifest documents submitted.
Basically, for generators of hazardous waste, the hazardous waste program fee is currently
determined as follows:
$1000.00 for generators of equal to or greater than 15 tons per year and less than
or equal to 100 tons per year of hazardous waste,
$6,000.00 for generators of greater than 100 tons per year and less than or equal to
500 tons per year of hazardous waste,
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$20,000.00 for generators of greater than 500 tons per year and less than 1,000 tons
per year of hazardous waste, and
• $40,000.00 for generators of greater than 1,000 tons per year.
In addition to the above, generators of equal to or greater than 15 tons per year of
hazardous -wastewater are assessed $3,000.00.
The use of a manifest New York State should only accompany shipments of hazardous
waste as defined under Part 371. In fact, Part 372.2(b)(6) states ..."Use of a Uniform Hazardous
Waste Manifest constitutes a determination by the generator that the solid waste is a hazardous
waste in New York and/or the state of generation."
Therefore, the utilization of a manifest accompanying a waste material that is clearly not
a hazardous waste material may be interpreted as a violation of New York State hazardous waste
regulations and therefore could be enforceable.
SUMMARY
We have just reviewed a number of regulatory and financial requirements mat generators
of hazardous waste in New York State and elsewhere across the country are obligated to comply
with in order to protect human health and environment. Presentations such as this are typically
offered to assist hazardous waste generators in achieving and maintaining regulatory compliance...
and thereby... minimize liability from regulatory violations and associated fines.
However, as we stated at the outset, the objective of this presentation is quite the opposite.
The focus here is to identify how one's liability is actually increased by utilizing the same
regulatory system discussed above (i.e. manifest document etc.) when it simply is not required
because the waste is not truly a hazardous waste.
Example. Facility A uses a water soluble alkaline powdered product to aid in degreasing
engine electric motors and transmission parts prior to rebuilding as part of its scheduled
maintenance program. Rather than establish a proper waste characterization program with
appropriate data quality objectives and quality assurance/quality control program, the facility
manager characterizes the spent solution as a characteristic hazardous waste and ships it off-site
via a licensed transporter with a signed manifest. The waste is characterized as corrosive
(D002). This practice continues for a number of years, with manifests documenting 10's of
thousands of gallons of "hazardous waste" being generated at the facility. (In fact, subsequent
analytical data and proper waste characterization determined the material not to be hazardous).
What are the liabilities associated with this scenario?
First, the use of a manifest signifies that the entity is a hazardous waste generator and,
as such, is required to comply with appropriate federal and state generator requirements. Most
important among these requirements is obtaining an EPA ID number. The ID number must be
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obtained by the generator in order to use a manifest. Now that you have declared generator
status, the following enforceable requirements are applicable:
• compliance with specific procedures for handling waste
• record keeping and reporting
. • proper labeling, marking and placarding
• develop and implement an emergency plan
• personnel training
• Preparedness and prevention measures
• annual generator report.
The above requirements are enforceable and may be subject to fine if determined not to
be satisfactory to government inspectors. However, if the generator manifests wastes as "non-
hazardous," the above requirements are not applicable.
Remember, the signature box on the manifest provides for a certification indicating that
the generator has a program in place to reduce the volume and toxicity of waste, and that the
method of treatment, storage or disposal Tninimiy.es present and future threats to human health
and the environment While these are commendable objectives, they are not applicable for a
small manufacturing facility that does not generate hazardous waste in the first place.
There are also hazardous waste reduction plan requirements. Hazardous waste manifest
documents are utilized to quantity the amounts of hazardous waste being generated at a facility.
This process can include an otherwise non hazardous waste generator on the list of hazardous
waste generators required by state law to prepare a Hazardous Waste Reduction Plan. The use
of manifests and the submission of annual generator reports at a facility that does not generate
hazardous waste in the first place can be an unnecessary regulatory burden. It costs resources to
develop, submit and implement a hazardous waste reduction plan.
Last but not least, there are the "waste end assessments" reportable and payable to the
Department of Taxation and Finance in New York State and regulatory fees assessed directly by
the Department of Environmental Conservation. While perhaps not perceived as an
overwhelming burden, when taken as a whole in consideration with the other prescribed
regulatory requirements, improper hazardous waste characterizations can take a bite from your
bottom line.
In short, the time, money and resources spent up front in proper waste characterizations
including the development and implementation of clear data quality objectives and a quality
assurance/quality control program, can go a long way toward reducing environmental compliance
and financial liability.
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References
Technical Assistance Document for Complying with the TC Rule and Implementing the
Toxicity Characteristic Leaching Procedure (TCLP), May 1993, US EPA Reg. n, DCN EPA 902-
br93-00i.
010RMW.RPT
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CD
O.
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Appendix XIV
Region II State TCLP Guidances
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State of New )eney
Department of Environmental Protection and Energy
Environmental Regulation
Hazardous Waste Regulation Program
CN421
Scott A. Weiner Trenton. NJ 08625-0421 Frank Coolick
Commissioner Phone* 609-633-1418 Adminisrrattjr
MEMORANDUM
M 04 1993
TO: Leon Lazarus, Environmental Scientist
USEPA, Monitoring Management Branch
FROM: Richard Johnson/ Supervising Env. Specialist
Bureau of Advisement and Manifest, DEPE
SUBJECT: Position Coordination for EPA's TCLP
Workshop on June 21, 1993
I. Spike Correction
On November 24, 1992, the Environmental Protection Agency
(EPA) removed the TCLP spike recovery correction and required
the method of standard additions be used for metals. This
change occurred at 40 CFR 261, Subpart D.
The New Jersey Department of Environmental Protection and
Energy (DEPE) requires that the test methods described in
Appendix II of 40 CFR 261, Subpart D be used for performing
the toxicity characteristic leaching procedure. Therefore,
since the quality control change has been completed at the
federal level, it is effective in New Jersey by reference.
II. Totals Analysis Versus TCLP Extract Analysis
This Bureau recommends following the guidance given in the
January 12, 1993 memo from the EPA Office of Solid Waste which
explains Section 1.2 of the TCLP. In brief, for hazardous
waste classification purposes, this Bureau will accept a total
constituent analysis value which has been divided by a factor
of twenty, in place of a TCLP value.
New jersey is an Iqual Opportunity Employer
Reeyded Paper
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However, our preference is the use of the TCLP instead of a
total constituent analysis for hazardous waste classification.
The reason for this is that a total constituent analysis such
as a priority pollutant analysis does not include all of the
TCLP constituents. ,A laboratory that submits a priority
pollutant -analysis in glace of a1 TCLP analysis, must be
careful to submit any: .add^ijonal analyses which might be
needed to compliment 'any missing anaiytes from the priority
pollutant test. The inclusion of these additional analyses
are usually omitted in packages which are. submitted to us,
which causes unnecessary delays in completing a
classification.
III. Status of EPA Land Ban Regulations in New Jersey
The EPA land ban regulations were authorized as part of the
EPA Hazardous and Solid Waste Amendments (HSWA). EPA will
enforce these requirements /imtil , New Jersey adopts this
regulation. Therefore, the EPA land ban requirements are
enforced at the federal level at this time. The DEPE is
planning to adopt ran equivalent set of regulations in the
future. When this occurs, DEPE personnel will enforce the
land ban requirements.
PR75(Sl):nb
c: John Barry, Enforcement, SFO
Tom Sherman, BHWE, DEPE
Phil Flax, HWCB,; DSEPA
Cathy Grimes, BEERA
Henry Hoffman, Laboratory Certification
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New York State Department of .Environmental Conservation
SO Wolf Road. Albany, New torfc 12233
Thomas C jortifi
CocnaUssionor
M EM O R A H D U M
TO: Distribution Below
FROM: r\ j^Noraan H. Nosenchucfc, Director _ —»*_
\\ff) Division of Hazardous Substances Regulation/::
VA - ' •••*-
SOBJECT:\\EPA Revised Disposal Standards for F001-FOOS Spent ^^~
'Solvent Wastes
DATE: JAN 2 1 »
The United States Environmental Protection Agency (EPA) has
.revised the disposal standards for the regulated hazardous
constituents of F001-F005 >spent solvent wastes.
These revisions were promulgated as part of the Land
Disposal Restrictions (LDRs) for Newly Listed Wastes and
Hazardous Debris that were published in the Federal Register on
August 18 / 1992. Due to the volume and widespread occurrence of
spent solvent wastes,, it was necessary to prepare this guidance,
as our Part 376 standards are now different from the revised 40
CFR 268 standards. The attached table will, for each
constituent, identify which agency's regulation is more stringent
and must be followed. Also included are the new standards as
they were promulgated by the EPA. This unfortunate but
unavoidable dual regulation will exist until the revised
standards can be adopted and promulgated by New York State.
current projections have this adoption of revisions at least 14
to 18 months away.
Other changes, and certain exclusions includedln"this final
rule, have created some confusion as to which agency's (EPA or
DEC) regulation is more stringent and/ therefore, the one to be
enforced. All newly listed wastes are unique to the federal
regulations.
If you have any questions concerning these revisions to the
LDRs, please contact Mr.. John D. Miccoli, of my staff, at
(518) 485-8988.
Attachment
Page 1 of 2
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PTs^RI BUT JL ON i
R. B«cherer, Region 1
S. Jagirdar, Region .2
A. Shah, Region 3
C. Van Guilder, Region 4
D. Curtis, Region 5
T. Morgan, Region 6
S. Eidt, Region 7
D. Rollins, Region 8
F. Shattuck, Region 9
bee: w/att: K, Nosenchuck (2)
H. O'Toole
D. Mafrici
L. Kadler
J. Hiddelkoop
P.. Counterman <^
R. Haggerty
J. Desai S
J. Miccoli/
JDM:NHN:gz
Page 2 of
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CONSTZTU2ST
WASTEWATER
NOHWASTEHATER
II Acetone [ 40 CFR Part 268
Benzene
n-Butyl alcohol
Carbon disulfide
1 Carbon tetrachloride
Chlorobenzene
Cresol (m-and-p isomers)
o-cresol
Cyclohexanone
o-Dichlorobenzene
Ethyl acetate
Ethyl benzene :
Ethyl ether
Ilsobutyl alcohol
Methanol
Methylene chloride
Methyl ethyl Ketone
Methyl isobutyl ketone
Nitrobenz ene
Pyridine
Tetrachloroethylene
Toluene
1,1, 1-Trichloroethane
1,1,2 -Tr ichloroethane
Same in both
40 CFR Part 268
Same in both
40 CFR Part 268
40 CFR Part 268
40 CFR Part 268
Part 376
Same in Both
40 CFR Part 268
Same in both
40 CFR Part 268
Part 376
40 CFR Part 268
' 40 CFR Part 268 I 40 CFR Part 268
Saae in both
40 CFR Part 268
40 CFR Part 268
40 CFR Part 268
40 CFR Part 268
40 CFR Part 268
Same in both
40 CFR Part 268
40 CFR Part 268
40 CFR Part 268
40 CFR Part 268
40 CFR Part 268
40 CFR Part 268
40 CFR Part 268
40 CFR Part 268
Same in both
Same in both
part 376
Part 376
Part 376
Part 376
Part 376
Same in both
Part 376
Part 376
Part 376
Part 376
Part 376
Part 376
Part 376
40 CFR Part 268
Same in both
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60'c
PO 01 -POOS SPgKT BOLVEKT ftgfiPIATm «a«*P««ns COK8TITPEKTS »
DISPOSAL
TO BE
COXSTZTUEKT
1,1, 2-Triehloro-l , 2 , 2-
trifluoroanethane
Trichloroethylcne
Trichloromono-
fluoronethane
Xylenes (total)
2-Nitropropane
2 -Etiioxyethamol ^
40 CFR Part 268
40 CFR Part 268
40 CFR Part 268
40 CFR Part 268
«
Sane in both
Same in both
Part 376
Part 376
Part 376
Part 376
Same in both
Same in both
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New York State Department of Environmental Conservation
50 Wolf Road, Albany. fttew Ybfk 12233
MEMORANDUM ThOWM C Jorttafi
CommtnteMT
TO: Distribution Below
FROM: Norman H. NosenchucJc, Director
Division of Hazardous Substances" Regulation
'SUBJECT: Revised Toxicity Characteristic Leaching Procedure
(TCLP)
: MAY 241993
The United States Environmental Protection Agency (EPA) has
revised the Toxicity Characteristic Leaching Procedure (TCLP) in
a revision to the Toxicity Characteristic (TC) rule.
The revision, promulgated on November 24, 1992, is the
result of the EPA's reassessment of the matrix spiXe correction
requirement, promulgated on June 29, 1990 as a final rule
technical correction to the TC rule. At that time, EPA's
intention was to achieve consistency with the SW-846 chapter One
requirements, proposed on February 8, 1990, which EPA anticipated
would be promulgated as a final rule prior to the effective date
of the TC rule.
However, to date, EPA has not promulgated the SW-846
Chapter One requirements. Therefore, in response to public
comments originally received on the February 8, 1990 proposed
changes, the EPA decided not to proceed with the proposed spike
recovery correction requirements for Subtitle C analytical
methods.
EPA stated in the November 24, 1992 preamble to their
revision that authorized states are given the option to adopt
this change to the TCLP procedure.
New York State, as did other states authorized for Land
Disposal Restrictions (LDR), included the TCLP as a requirement
to implement these LDR regulations. As part of our current
rulemaking process to update our hazardous waste regulations, we
will include the revised TCLP for the TC rule and the LDR
regulations.
Page. 1 of 2
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In the meantime, to eliminate confusion regarding specific
in the TCLP testing methods in the interim, DEC will accept the
EPA version currently in place as Appendix II to 40 CFR Part 261,
designated as Method 1311, as an alternative to the TCLP
(Appendix 35) currently found in Part 376 to implement the LDRs.
Attached for your convenience and use, is both a copy of the
Federal Register notice of November 24, 1992, and the draft
changes to Appendix 35 found in Part 376. The draft Appendix 35,
Section 8.0 - Quality Assurance, has brackets [ ] surrounding
words or formulas being removed, and underlines all additions.
Please call John D. Miccoli, of my staff, at (518) 485-8988
if you have any guestions concerning the possible ramifications
of this change to our LDR program.
Attachment
PTSTRIBPTTON ;
R. Beeherer, Region 1
S. jagirdar, Region 2 .
R. Aldrich, Region 3
C, van Guilder, Region 4
D. Curtis, Region 5
T. Morgan, Region 6
S. Eidt, Region 7
D. Rollins, Region 8
F. Shattucfc, Region 9
cc: w/att: E. Sullivan
N.G. Kaul
M. O'Toole
. G. Kelly
face: w/att: N. Nosenchuck (2)
D. Mafrici
L. Nadler
D. Aldrich
J. MiddeDcoop
P .
R. Haggerty
J. Desai
J. Miccoli
JDK:DLA:MHN:gz
Page 2 of 2
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